Furochroman derivatives

ABSTRACT

Disclosed are furochroman compounds of formula I 
     
       
         
         
             
             
         
       
     
     liquid-crystal media which contains the compounds of formula I, and the use of the media in electro-optical displays, in particular in VAN LCDs.

The present invention relates to furochroman derivatives, preferably mesogenic furochroman derivatives, in particular liquid-crystalline furochroman derivatives, and to liquid-crystalline media comprising these furochroman derivatives. The present invention furthermore relates to liquid-crystal displays, in particular active matrix addressed liquid-crystal displays (AMDs or AM LCDs) and very particularly so-called VAN (“vertically aligned nematic”) liquid-crystal displays, an embodiment of ECB (“electrically controlled birefringence”) liquid-crystal displays, in which nematic liquid crystals of negative dielectric anisotropy (Δ∈) are used.

In liquid-crystal displays of this type, the liquid crystals are used as dielectrics, whose optical properties change reversibly on application of an electric voltage. Electro-optical displays which use liquid crystals as media are known to the person skilled in the art. These liquid-crystal displays use various electro-optical effects. The commonest thereof are the TN (“twisted nematic”) effect, with a homogeneous, virtually planar initial alignment of the liquid-crystal director and a nematic structure which is twisted by about 90°, the STN (“super-twisted nematic”) effect and the SBE (“supertwisted birefringence effect”) with a nematic structure which is twisted by 180° or more. In these and similar electro-optical effects, liquid-crystalline media of positive dielectric anisotropy (Δ∈) are used.

Besides the said electro-optical effects, which require liquid-crystal media of positive dielectric anisotropy, there are other electro-optical effects which use liquid-crystal media of negative dielectric anisotropy, such as, for example, the ECB effect and its sub-forms DAP (“deformation of aligned phases”), VAN and CSH (“colour super homeotropics”).

An electro-optical effect having excellent, low viewing-angle dependence of the contrast uses axially symmetrical micropixels (ASMs). In this effect, the liquid crystal of each pixel is surrounded in a cylindrical manner by a polymer material. This mode is particularly suitable for combination with addressing through plasma channels. Thus, in particular, large-area PA (“plasma addressed”) LCDs having good viewing-angle dependence of the contrast can be achieved.

The IPS (“in plane switching”) effect employed to an increased extent recently can use both dielectrically positive and also dielectrically negative liquid-crystal media, in a similar manner to “guest/host” displays, which can employ dyes either in dielectrically positive or dielectrically negative media, depending on the display mode used.

Since the operating voltage in liquid-crystal displays in general, i.e. also in displays utilising these effects, should be as low as possible, use is made of liquid-crystal media having a large absolute value of the dielectric anisotropy which generally predominantly and in most cases even essentially consist of liquid-crystal compounds having a dielectric anisotropy having the corresponding sign, i.e. of compounds of positive dielectric anisotropy in the case of dielectrically positive media and of compounds of negative dielectric anisotropy in the case of dielectrically negative media. In the respective types of media (dielectrically positive or dielectrically negative), at most significant amounts of dielectrically neutral liquid-crystal compounds are typically employed. Liquid-crystal compounds having the opposite sign of the dielectric anisotropy to that of the dielectric anisotropy of the medium are generally employed extremely sparingly or not at all.

An exception is formed here by liquid-crystalline media for MIM (“metal-insulator-metal”) displays (Simmons, J. G., Phys. Rev. 155, 3, 657-660 and Niwa, J. G. et al., SID 84 Digest, 304-307, June 1984), in which the liquid-crystal media are addressed by means of an active matrix of thin-film transistors. In this type of addressing, which utilises the nonlinear characteristic line of diode switching, a storage capacitor cannot be charged together with the electrodes of the liquid-crystal display elements (pixels), in contrast to TFT displays. In order to reduce the effect of the drop in voltage during the addressing cycle, the largest possible base value of the dielectric constant is thus necessary. In the case of dielectrically positive media, as employed, for example, in MIM-TN displays, the dielectric constant perpendicular to the molecular axis (∈_(⊥)) must thus be as large as possible since it determines the basic capacitance of the pixel. To this end, as described, for example, in WO 93/01253, EP 0 663 502 and DE 195 21 483, compounds of negative dielectric anisotropy are simultaneously also employed besides dielectrically positive compounds in the dielectrically positive liquid-crystal media.

A further exception is formed by STN displays, in which, for example, dielectrically positive liquid-crystal media in accordance with DE 41 00 287 comprising dielectrically negative liquid-crystal compounds are employed in order to increase the steepness of the electro-optical characteristic line.

The pixels of the liquid-crystal displays can be addressed directly, time-sequentially, i.e. in time multiplex mode, or by means of a matrix of active elements having nonlinear electrical characteristic lines.

The commonest AMDs to date use discrete active electronic switching elements, such as, for example, three-pole switching elements, such as MOS (“metal oxide silicon”) transistors or thin film transistors (TFTs) or varistors, or 2-pole switching elements, such as, for example, MIM (“metal-insulator-metal”) diodes, ring diodes or “back-to-back” diodes. Various semiconductor materials, predominantly silicon, but also cadmium selenide, are used in the TFTs. In particular, amorphous silicon or polycrystalline silicon is used.

In accordance with the present application, preference is given to liquid-crystal displays having an electric field perpendicular to the liquid-crystal layer and liquid-crystal media of negative dielectric anisotropy (Δ∈<0). In these displays, the edge alignment of the liquid crystals is homeotropic. In the fully switched-through state, i.e. on application of an electric voltage of appropriate magnitude, the liquid-crystal director is aligned parallel to the layer plane.

Chroman derivatives and the use thereof as a component in liquid-crystal mixtures are described in the specification EP 1 491 612 A1.

The use of benzofurans or dihydrobenzofurans in liquid-crystal mixtures is described in the specification DE 199 00 517 A1.

Furthermore, it is pointed out in the literature [M. Bremer, L. Lietzau, New. J. Chem. 2005, 29, 72-74] that the introduction of an alkoxy side chain fixed to the aromatic ring into liquid crystals based on the 2,3-difluorophenyl unit, such as, for example, into benzofurans or dihydrobenzofurans, gives compounds having comparatively high polarity.

The development in the area of liquid-crystalline materials is still far from complete. In order to improve the properties of liquid-crystalline display elements, attempts are constantly being made to develop novel compounds which enable optimisation of displays of this type.

It is therefore an object of the present invention to provide compounds having advantageous properties for use in liquid-crystalline media. They should preferably have negative dielectric anisotropy (Δ∈<0), which makes them particularly suitable for use in liquid-crystalline media for VA displays. In order to guarantee satisfactory properties, in particular low characteristic voltages, in, for example, VA-TFT displays, substances having a large absolute value of the dielectric anisotropy (Δ∈), a value of the optical anisotropy (Δn) which corresponds to the particular application, and good stability to UV, heat and electric voltage are required.

This is achieved by the use of the compounds of the formula I according to the invention

-   -   in which     -   R¹ and R² each, independently of one another, denote H, halogen,         —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂ or an alkyl         group having 1 to 15 C atoms, which may optionally be         monosubstituted by CN or CF₃ or at least monosubstituted by         halogen and in which one or more CH₂ groups, in each case         independently of one another, may in each case be replaced by         —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

-   -    —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither 0         nor S atoms are linked directly to one another,     -   one of the radicals R¹ and R² preferably denotes alkyl or alkoxy         having 1 to 12 C atoms, alkoxyalkyl, alkenyl or alkenyloxy         having 2 to 12 C atoms, and the other, independently of the         first, likewise denotes alkyl or alkoxy having 1 to 12 C atoms,         alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 C atoms or         alternatively F, Cl, Br, —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F,         —OCF₃ or —OCHF₂,     -   >Y¹—Y²— denotes >C═CH— or >CH—CH₂—, preferably >C═CH—,     -   L¹ and L² each, independently of one another, denote H, halogen,         —CN or —CF₃, preferably H, F or Cl, particularly preferably H or         F and very particularly preferably F,

each, independently of one another, and, if present more than once, these also independently of one another, denote

-   -   (a) a trans-1,4-cyclohexylene radical, in which, in addition,         one or two non-adjacent CH₂ groups may be replaced by —O— and/or         —S—,     -   (b) a 1,4-cyclohexenylene radical,     -   (c) a 1,4-phenylene radical, in which, in addition, one or two         non-adjacent CH groups may be replaced by N,     -   (d) a radical selected from the group naphthalene-2,6-diyl,         decahydronaphthalene-2,6-diyl and         1,2,3,4-tetrahydronaphthalene-2,6-diyl, or     -   (e) a radical selected from the group         1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene and         spiro[3.3]heptane-2,6-diyl, where in         -   (a) and (b), one or more —CH₂— groups, independently of one             another, may each be replaced by a —CHF— or a —CF₂— group,             and in         -   (c) and (d), one or more —CH═ groups, independently of one             another, may each be replaced by a group selected from the             group —CF═, —CCl═, —CBr═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═,             —C(CHF₂)═, —C(OCH₃)═, —C(OCHF₂)═ and —C(OCF₃)═, preferably a             —CF═ group, and preferably

-   -   -    particularly preferably

denotes

-   -   -    particularly preferably

denotes

-   -   Z¹ and Z² each, independently of one another, and, if present         more than once, these also independently of one another, denote         a single bond, —CH₂—CH₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CF₂—CF₂—,         —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—,         —OCH₂—, —CF₂O—, —OCF₂—, or a combination of two of these groups,         where no two O atoms are bonded to one another,     -   preferably —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—,         —C≡C—, —CH₂O—, —CF₂O— or a single bond,     -   particularly preferably —CH₂O—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—,         —CF₂O— or a single bond, and     -   n and m each denote 0, 1, 2 or 3, where     -   (n+m) denotes 0, 1, 2 or 3, preferably 0, 1 or 2, particularly         preferably 0 or 1.

The compounds of the formula I according to the invention are preferably mesogenic compounds and particularly preferably liquid-crystalline compounds.

Compounds of the formula I according to the invention are particularly preferably selected from the sub-formulae IA and IB (where IA: >Y¹—Y²⁻═>C═CH— and IB: >Y¹—Y²⁻═>CH—CH₂—):

-   -   in which the parameters have the respective meanings given above         under formula I.

Preference is given to compounds of the formula I which are preferably selected from the group of the compounds of the formulae IA and IB in which the sum n+m is 0, 1 or 2, particularly preferably 0 or 1.

A preferred embodiment is represented by the compounds of the formula I in which the sum n+m is 1, and preferably

denotes

 particularly preferably

denotes

 particularly preferably

denotes

-   Z¹, Z² preferably denote —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—,     —CF═CF—, —C≡C—, —O—CH₂—, —O—CF₂— or a single bond, particularly     preferably —O—CH₂—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—, —O—CF₂— or a     single bond, and -   L¹, L², R¹ and R² have the meanings given above under formula I, and -   L¹ and L² preferably denote F.

Particular preference is given to compounds of the formula I which are preferably selected from the group of the compounds of the formulae IA and IB in which

n and m both denote 0, and L¹, L², R¹ and R² have the meanings given above under the corresponding formula, and L¹ and L² preferably denote F.

Particular preference is given to compounds of the formula IA which are selected from the group of the compounds of the formulae IA-1 to IA-11, preferably of the formulae IA-1 to IA-6, particularly preferably of the formulae IA-1 to IA-3, IA-5 and IA-6, in which at least one of the groups R¹ and R² is linked directly to the skeleton:

-   -   in which the parameters have the respective meanings given         above.

Here, as throughout the present application, the group of the sub-formula I-1

-   -   in which the parameters have the meanings given above, and         preferably     -   >Y¹—Y² denotes >C═CH—,         is referred to as the skeleton of the compounds of the formula         I, or for short as the skeleton.

Particular preference is given to compounds of the formula IB which are selected from the group of the compounds of the formulae IB-1 to IB-11, preferably of the formulae IB-1 to IB-6, particularly preferably of the formulae IB-1 to IB-3, IB-5 and IB-6, in which at least one of the groups R¹ and R² is linked directly to the skeleton:

-   -   in which the parameters have the respective meanings given         above.

Particular preference is given to compounds of the formula I which have one or more fluorine substituents, very particularly preferably two fluorine substituents, in the skeleton.

Compounds of the formula I containing branched wing groups R¹ and/or R² may occasionally be of importance owing to better solubility in the usual liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials. Compounds of the formula I having SA phases are suitable, for example, for thermally addressed displays.

If R¹ and/or R² denote an alkyl radical and/or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

Oxaalkyl or alkoxyalkyl preferably denotes straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by —CH═CH—, this may be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. Accordingly, it denotes, in particular, vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by —O— and one has been replaced by —CO—, these are preferably adjacent. These thus contain an acyloxy group —CO—O— or an oxycarbonyl group —O—CO—. These are preferably straight-chain and have 2 to 6 C atoms.

Accordingly, they denote, in particular, acetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetoxypropyl, 3-propionyloxypropyl, 4-acetoxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl or 4-(methoxycarbonyl)butyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by unsubstituted or substituted —CH═CH— and an adjacent CH₂ group has been replaced by CO or CO—O or O—CO, this may be straight-chain or branched. It is preferably straight-chain and has 4 to 13 C atoms. Accordingly, it denotes, in particular, acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloyloxynonyl.

If R¹ and/or R² denote an alkyl or alkenyl radical which is monosubstituted by CN or CF₃, this radical is preferably straight-chain. The substitution by CN or CF₃ is in any desired position.

If R¹ and/or R² denote an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain, and halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the ω-position.

Branched groups generally contain not more than one chain branch. Preferred branched radicals R are isopropyl, 2-butyl (=1-methylpropyl), isobutyl (=2-methylpropyl), 2-methylbutyl, isopentyl (=3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy, 1-methylhexyloxy and 1-methylheptyloxy.

If R¹ and/or R² represent an alkyl radical in which two or more CH₂ groups have been replaced by —O— and/or —CO—O—, this may be straight-chain or branched. It is preferably branched and has 3 to 12 C atoms. Accordingly, it denotes, in particular, biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biscarboxypropyl, 4,4-biscarboxybutyl, 5,5-biscarboxypentyl, 6,6-biscarboxyhexyl, 7,7-biscarboxyheptyl, 8,8-biscarboxyoctyl, 9,9-biscarboxynonyl, 10,10-biscarboxydecyl, bis(methoxycarbonyl)methyl, 2,2-bis(methoxycarbonyl)ethyl, 3,3-bis(methoxycarbonyl)propyl, 4,4-bis(methoxycarbonyl)butyl, 5,5-bis(methoxycarbonyl)pentyl, 6,6-bis(methoxycarbonyl)hexyl, 7,7-bis(methoxycarbonyl)heptyl, 8,8-bis(methoxycarbonyl)octyl, bis(ethoxycarbonyl)methyl, 2,2-bis(ethoxycarbonyl)ethyl, 3,3-bis(ethoxycarbonyl)propyl, 4,4-bis(ethoxycarbonyl)butyl or 5,5-bis(ethoxycarbonyl)pentyl.

Especial preference is given to compounds of the formula I in which one of the parameters m and n has the value 0 and the other has a value as defined above, preferably >0, and to media comprising these compounds. Particularly preferably, therefore, m=0 and n=0, 1 or 2 or n=0 and m=0, 1 or 2, where R¹ and/or R² preferably denote methyl, ethyl, propyl, butyl, pentyl, vinyl, 1E-propenyl, 1E-butenyl or 1E-pentenyl.

Especial preference is also given to compounds of the formula I which carry one or more alkenyl substituents.

Owing to asymmetrically substituted carbon atoms in the ring B, the compounds of the formula I can be in the form of stereoisomers. The invention relates to all isomers, both in pure form, as the racemate and also as a mixture of diastereomers or enantiomers. Optically active compounds of the formula I can also be used as dopants in liquid-crystal mixtures.

In the following schemes, the compounds of the formula IA are referred to for short as compounds 1 and those of the formula IB are referred to for short as compounds 2. For better legibility of the formulae, however, the square brackets and the parameters n and m are omitted. The rings A¹ and A² can thus also have the meaning of a single bond; and one of the groups A¹-Z¹ and A²-Z² may also in each case occur twice, in which case the parameters which then occur twice may in each case, independently of one another, have one of the meanings indicated.

The compounds of the formula I are synthesised by two conceptually different routes. In the first route, route A (cf. scheme 1), the chroman structure is prespecified, and the furan moiety is built up starting from the former. For this purpose, suitable substituted 5-halochroman-6-ols 7 (X=Br, I) are used as synthetic building blocks. Sonogashira coupling to appropriately substituted terminal alkynes 8 generally proceeds with direct cyclisation and gives the compounds 1 of the formula I [DE 199 00 517 A1 and G. A. Gfesser, R. Faghih, Y. L. Bennani, M. P. Curtis, T. A. Esbenshade, A. A. Hancock, M. D. Cowart, Biorg. Med. Chem. Lett. 2005, 15, 2559-2563]. Depending on the nature of the alkyne 8, the conversion into the compounds 1 is advantageously carried out in two steps. Under the conditions of the Sonogashira coupling, the compounds 9 are firstly obtained as intermediates here. The cyclisation is then carried out on treatment with diethylzinc [M. Nakmura, L. Ilies, S. Otsubo, E. Nakamura, Angew. Chem. 2006, 118, 958-961; Angew. Chem. Int Ed. 2006, 45, 944-947].

in which, as in the following schemes, unless explicitly indicated otherwise, the parameters have the respective meaning given above.

For the second route, route B (cf. scheme II), 2-substituted benzofuran-5-ols 10 are used as central intermediates. Compounds of type 1 are then obtained by anellation of a pyran ring. Starting from 10, this can either be carried out via a Claisen rearrangement [H. Ishii, T. Ishikawa, S. Takeda, S. Ueki, M. Suzuki, Chem. Pharm. Bull. 1992, 40, 1148-1153] or a reaction described by Wang and Finn [Q. Wang, M. G. Finn, Org. Lett. 2000, 2, 4063-4065].

The starting materials 14 for a Claisen rearrangement are obtained from 10 by Mitsunobu etherification [O. Mitsunobu, Synthesis 1981, 1] using propargyl alcohols 12, which are accessible, for example, by the addition reaction of lithium acetylide onto a corresponding aldehyde. On heating in N,N-diethylaniline, the aryl propargyl ethers 14 undergo a [3.3]-sigmatropic rearrangement to give the chromene derivatives 15. These can alternatively be synthesised from the salicylaldehyde derivatives 11. The compounds 11 are obtained by suitable formylation (cf. scheme II) of the benzofuran-5-ols 10. Conversion into the chroman 15 takes place via coupling to vinylboronic acids 13 [Q. Wang, M. G. Finn, Org. Lett. 2000, 2, 4063-4065]. Finally, the chromene double bond of the compounds 15 is selectively hydrogenated under mild conditions.

Compounds of type 2 are obtained directly from compounds of type 1 by hydrogenation of the 1,2-double bond (cf. scheme III).

Alternatively, dihydrobenzofuranols 16 can also be utilised as starting materials for the synthesis of the compounds 2 (cf. scheme IV).

The synthesis can be adapted to the compounds of the formula I desired in each case through the choice of suitable starting materials 7 and 8 (route A, cf. scheme 1) or 10 and 12 or 13 (route B, cf. scheme II). The compounds of the formula II are then either obtained from the compounds 1 (cf. scheme III) or can be adapted to the compounds of the formula II desired in each case through the choice of suitable starting materials 16 and 12 or 13 (cf. scheme IV).

The starting materials 8 (route A, cf. scheme II), 12 and 13 (route B, cf. scheme II and scheme IV) are either commercially available or can be synthesised following processes that have already been published [for example Methoden der organischen Chemie [Methods of Organic Chemistry] (Houben-Weyl), Georg Thieme Verlag, Stuttgart, N.Y., 4th Edn. 1993].

The substitution pattern with respect to the radicals L¹ and L² in some cases makes particular requirements of the synthesis of the starting materials 7 (route A, cf. scheme 1), 10 (route B, cf. scheme II) and 16 (cf. scheme IV).

7,8-Difluoro-5-halochroman-6-ols 26 (X=Br, I, cf. scheme VI) are synthesised starting from 2,3-difluorophenol (20) or 3,4-difluoro-2-hydroxybenzaldehyde (23) [N. J. Lawrence, L. A. Hepworth, D. Rennison, A. T. McGown, J. A. Hadfield, J. Fluorine Chem. 2003, 123, 101-108 and E. Marzi, J. Gorecka, M. Schlosser, Synthesis 2004, 1609-1618] (cf. scheme V).

To this end, a propargyl aryl ether 21 is firstly formed from 2,3-difluorophenol (20) and a propargyl alcohol 12 by Mitsunobu etherification [O. Mitsunobu, Synthesis 1981, 1-28] and then undergoes a thermal [3.3]-sigmatropic rearrangement under suitable reaction conditions to give a 2H-chromene. These chromenes can easily be hydrogenated under gentle conditions to give the corresponding chromans 22.

Alternatively, these 7,8-difluorochromans 22 are obtained from 3,4-difluoro-2-hydroxybenzaldehyde (23) [N. J. Lawrence, L. A. Hepworth, D. Rennison, A. T. McGown, J. A. Hadfield, J. Fluorine Chem. 2003, 123, 101-108 and E. Marzi, J. Gorecka, M. Schlosser, Synthesis 2004, 1609-1618] via a reaction described by Wang and Finn [Q. Wang, M. G. Finn, Org. Lett. 2000, 2, 4063-4065]. 2H-chromenes, such as 24, are obtained in high yield here from salicylaldehydes and vinylboronic acids in the presence of dibenzylamine and can then in turn easily be hydrogenated to give the corresponding chromans 22 (see above).

The intermediates 22 obtained in this way are functionalised by ortho-metallation and hydrolysis and oxidation of the boronic acid ester formed in situ to give chromanols 25 (cf. scheme VI). Final halogenation of the 5-position takes place via the reaction sequence depicted in scheme VI. The MOM ethers prepared from the compounds 25 are ortho-metallated using n-BuLi and quenched using iodine (or bromine for X=Br) [E. Marzi, J. Gorecka, M. Schlosser, Synthesis 2004, 1609-1618 and R. C. Ronald, M. R. Winkle, Tetrahedron 1983, 39, 2031-2042 and M. Lang, W. Steglich, Synthesis 2005, 1019-1027]. Removal of the MOM group gives the desired intermediates 26.

7-Fluoro-5-halochroman-6-ols 31 (X=Br, I) can be synthesised from 5-bromo-4-fluoro-2-hydroxybenzaldehyde (27) [J. B. Blair et al., J. Med. Chem. 2000, 43, 4701-4710 and W. A. Caroll et al., J. Med. Chem. 2004, 47, 3163-3179] (cf. scheme VII). This starting material 27 is accessible via processes known from the literature from 3-fluorophenol by ortho-selective formylation [J. B. Blair et al., J. Med. Chem. 2000, 43, 4701-4710] and subsequent bromination [W. A. Caroll et al., J. Med. Chem. 2004, 47, 3163-3179].

Starting from 5-bromo-4-fluoro-2-hydroxybenzaldehyde (27), the synthesis of the 7-fluorochromans 31 (cf. scheme VII) is in turn advantageously carried out by the coupling to vinylboronic acids already described [Q. Wang, M. G. Finn, Org. Lett. 2000, 2, 4063-4065] and subsequent hydrogenation. The functionalisation to give the chromanol 30 is carried out as described above, this time via the Grignard compound formed from 29. Final iodination (or bromination) can be carried out as above via the MOM ethers of the compounds 30, but is advantageously also carried out by direct iodination [G. A. Gfesser, R. Faghih, Y. L. Bennani, M. P. Curtis, T. A. Esbenshade, A. A. Hancock, M. D. Cowart, Biorg. Med. Chem. Lett. 2005, 15, 2559-2563, M. Lang, W. Steglich, Synthesis 2005, 1019-1027 and C. W. Holzapfel, D. B. G. Williams, Tetrahedron 1995, 51, 8555-8564, K. J. Edgar, S. N. Falling, J. Org. Chem. 1990, 55, 5287-5291 and R. Johnsson, A. Meijer, U. Ellervik, Tetrahedron 2005, 61, 11567-11663] (or bromination [B. F. Bonini, P. Carboni, G. Gottarelli, S. Masiero, G. P. Spada, J. Org. Chem. 1994, 59, 5930-5936]) of the chromanols 30.

8-Fluoro-5-halochroman-6-ols 36 (where X=Br, I) are obtained starting from 2-fluoro-4-bromophenol (32). Here, the O-heterocycle is preferably anellated by a Claisen rearrangement via the propargyl aryl ethers 33 (cf. scheme VIII). The functionalisation to give the chromanol 35 is carried out with the same reaction sequence as for the regioisomer 29. The halogenation of 35 gives principally the desired isomers 36 (X=Br, I), which can be separated off from undesired regioisomers via laboratory-typical purification methods.

Alternatively, the intermediates 34 can also be synthesised starting from 2-fluoro-4-bromophenol (32) via the salicylaldehyde 37. The latter is accessible from 32 via a Duff reaction [M. L. Micklatcher, M. Cushman, Synthesis 1999, 1878-1880]. The subsequent synthesis of the chroman 34 can then be carried out via the procedure described by Wang and Finn [Q. Wang, M. G. Finn, Org. Lett. 2000, 2, 4063-4065] and subsequent hydrogenation (scheme IX).

Non-fluorinated synthetic building blocks 41 can likewise be synthesised by the methods described above (Claisen rearrangement or coupling to vinylboronic acids). A particularly preferred process starts from 2,5-dihydroxybenzaldehyde (38), which is firstly brominated by methods known from the literature [Y. Hu, C. Li, B. A. Kulkarni, G. Strobel, E. Lokovsky, R. M. Torczynski, J. A. Porco, Org. Lett. 2001, 3, 1649-1652] and selectively protected (cf. scheme X). After two-step conversion into the chroman 40, removal of the TBS group gives the bromide 41 (X=Br), which serves as starting material for the subsequent Sonogashira couplings. In some cases, the Sonogashira coupling to corresponding aryl iodides 41 (X=I) is particularly advantageous. These compounds 41 (X=I) are likewise accessible from the bromochroman 40 via the reaction sequence depicted in scheme X comprising halogen-metal exchange, scavenging using iodine and removal of the protecting group using fluoride.

Suitable substituted 6,7-difluorobenzofuran-5-ols 46 and 6,7-difluoro-2,3-dihydrobenzofuran-5-ols 47 can be obtained as follows (scheme XI).

2,3-Difluoro-6-halophenols 42 are advantageously synthesised from 2,3-difluorophenol (20) via the reaction sequence already explained. The 2-substituted benzofurans 44 are either formed directly in a Sonogashira coupling to a suitable alkyne 8 or are obtained via the intermediate 43 and subsequent cyclisation using diethylzinc (cf. scheme 1). These benzofurans 44 can readily be hydrogenated to the corresponding dihydrobenzofurans 45. The 6,7-difluorobenzofuran-5-ols 46 or 6,7-difluoro-2,3-dihydrobenzofuran-5-ols 47 necessary for the reaction sequences depicted in scheme II and scheme IV are obtained from 44 or 45 respectively by ortho-metallation, hydrolysis and oxidation of the boronic acid ester formed in situ.

6-Fluorobenzofuran-5-ols 53 (where L¹=H and L²=F) or 6-fluoro-2,3-dihydrobenzofuran-5-ols 54 (where L¹=H and L²=F), 7-fluorobenzofuran-5-ols 53 (where L¹=F and L²=H) or 7-fluoro-2,3-dihydrobenzofuran-5-ols 54 (where L¹=F and L²=H) and benzofuran-5-ols 53 (where L¹=H and L²=H) or 2,3-dihydrobenzofuran-5-ols 54 (where L¹=H and L²=H) can be prepared by conceptually similar routes. In contrast to the above, corresponding 4-bromophenols 48 are selected as starting materials. The functionalisation to give the benzofuranols 53 and 54 is then not carried out by ortho-metallation, but instead via the Grignard reagents obtained from compounds 51 and 52 (cf. scheme XII).

For the specific case where R¹A¹Z¹A¹Z¹ denotes methyl and L¹ and L² denote F, a suitably functionalised benzofuran 60 can be prepared particularly simply via a [3.3]-sigmatropic rearrangement starting from 56 (cf. scheme XIII). 56 is prepared from 5-bromo-2,3-difluorophenol (55) and propargyl bromide. Heating in N,N-diethylaniline in the presence of caesium fluoride [H. Ishii, T. Ishikawa, S. Takeda, S. Ueki, M. Suzuki, T. Harayama, Chem. Pharm. Bull. 1990, 38, 1775-1777 and A. Chilin, P. Rodighiero, A. Guiotto, Synthesis 1998, 309-312] gives the benzofuran 57. The functionalisation to give the salicylaldehyde 60 is then carried out via a combination of the standard methods already explained above. The sub-sequent procedure can then be carried out as depicted above in scheme II.

For compounds of the formula I (1 and 2) in which R¹A¹Z¹A¹Z¹ and/or R²A²Z² A²Z² represent, in particular, an alkenyl radical or another mono- or polyunsaturated radical, the following processes (schemes XIV to XVII) are particularly preferred.

A first preferred process, for the synthesis of compounds 1 and 2 in which R¹A¹Z¹A¹Z¹ represents, in particular, one or more alkenyl radicals or another mono- or polyunsaturated radical, again starts from 5-halo-chroman-6-ols 7 (scheme XIV).

If the sequence comprising Sonogashira coupling and ring closure using THP-protected homopropargyl alcohol 61 [N. G. Kundu, M. Pal, J. S. Mahanty, M. De, J. Chem. Soc. Perkin Trans 11997, 19, 2815-2820] is carried out, the compounds 62 are obtained. Starting from the latter, cleavage of the THP ether and oxidation of the resultant primary alcohol [L. Capuano, S. Drescher, V. Hammerer, M. Hanisch, Chem. Ber. 1988, 121, 2259-2262] can give the functionalisable intermediate 64. Functionalisation thereof to give the compounds 1 can then be carried out, for example, by Wittig olefination (cf. scheme XV). A functionalisable intermediate 65 which results in the compounds 2 in this way (Wittig olefination, etc.) is obtained after hydrogenation of 62 to 63, subsequent THP cleavage and oxidation.

If it is intended to synthesise compounds of type 1 in which R¹Z¹A¹Z¹A¹ and R²A²Z²A²Z² contain unsaturated radicals, bridges or ring systems, correspondingly substituted 5-halochroman-6-ols 70 can be employed. The latter are accessible via the following process (cf. scheme XV) using the chroman-2-carbaldehydes 69 as central, functionalisable intermediates. Starting from salicylaldehydes 66 (Y=H, Br, cf. schemes V, VII and IX), the chromene 68 is built up with the boronic acid 67 [R. A. Batey, A. N. Avinash, A. J. Lough, J. Am. Chem. Soc. 1999, 121, 450-451]. Hydrogenation and oxidation gives the intermediate 69. Starting from the latter, the R²A²Z²A²Z² side chain can firstly then be built up; the subsequent functionalisation to give the 5-halochroman-6-ols 70, which can then be converted into the compounds 1 in accordance with scheme XIV, has already been described (cf. schemes V, VII and IX).

These substances are also suitable for the synthesis of compounds 2 in which R¹Z¹A¹Z¹A¹ and R²A²Z²A²Z² contain unsaturated radicals, bridges or ring systems. To this end, the following process is required in accordance with the literature procedure [J. C. González-Gómez, L. Santana, E. Uriarte, Tetrahedron 2005, 61, 4805-4810 and K. J. Hodgetts, Tetrahedron 2005, 61, 6860-6870] (cf. scheme XVI).

Etherification of 7 (X=Br is particularly preferred) using the bromoethanol derivatives 71 gives the compounds 72 (X=Br). The Grignard reagent generated from the compounds 72 cyclises spontaneously under the reaction conditions with formation of a 5-membered heterocycle.

If it is intended to synthesise compounds 1 and 2 in which R²A²Z² A²Z² contains unsaturated radicals, bridges or ring systems, processes which use functionalisable intermediates such as 74 and 75 are preferred.

Starting from the salicylaldehyde derivatives 11 which have already been described above, the pyran moiety is built up using the boronic acid 67 [R. A. Batey, A. N. Avinash, A. J. Lough, J. Am. Chem. Soc. 1999, 121, 450-451] (cf. scheme XV). The chromene CC double bond is hydrogenated under mild conditions (1 atm of H₂, room temperature), and the benzyl ether is cleaved to give the corresponding alcohol. It is only at increased hydrogen pressure and elevated temperature that the hydrogenation of the 2,3-double bond also takes place. The alcohols formed are oxidised to the corresponding aldehydes, and the compounds 74 and 75 can then be functionalised to give compounds 1 and 2 as depicted, for example, in scheme XV.

Examples of structures of preferred compounds of the formula I are given below in sub-formula order,

in which

-   R¹¹ and R²² have the respective meaning given under formula I for R¹     and R² respectively, -   p, and in the case where p occurs more than once, these     independently of one another,     -   denotes 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and preferably

Of the compounds IA-1 to IA-11 and IB-1 to IB-11, particular preference is given to those having at least one fluorine substituent in the skeleton.

Very particular preference is given to compounds having two fluorine substituents in the skeleton.

Preferred compounds of the formulae IA-1 and IB-1 are:

Preferred compounds of the formulae IA-2 and IB-2 are:

Of the compounds IA-2 and IB-2, particular preference is given to those containing a cyclohexyl ring.

Preferred compounds of the formulae IA-3 and IB-3 are:

Of the compounds of the formula IA-3, compounds containing an unsubstituted or substituted 1,4-phenylene ring are preferred.

Of the compounds IB-3, particular preference is given to those containing a cyclohexyl ring.

Preferred compounds of the formulae IA-4 and IB-4 are:

Of the compounds of the formula IA-4, particular preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by a substituted or unsubstituted 1,4-phenylene ring and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Of the compounds of the formula IB-4, preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by a cyclohexyl radical and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Preferred compounds of the formulae IA-5 and IB-5 are:

Of the compounds IA-5 and IB-5, preference is given to those containing a cyclohexyl ring. Particular preference is given here to compounds in which a cyclohexyl ring is linked directly to the skeleton. Very particular preference is given to compounds containing two cyclohexyl rings.

Preferred compounds of the formulae IA-6 and IB-6 are:

Of the compounds IA-6, preference is given to those containing an unsubstituted or substituted 14-phenylene ring. Particular preference is given here to compounds in which an unsubstituted or substituted 1,4-phenylene ring is linked directly to the skeleton.

Of the compounds IB-6, preference is given to those containing a cyclohexyl ring. Particular preference is given here to compounds in which a cyclohexyl ring is linked directly to the skeleton.

Of the compounds of the formula IA-7, preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by an aryl radical and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Of the compounds of the formula IB-7, preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by a cyclohexyl radical and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Of the compounds of the formula IA-8, preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by an aryl radical and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Of the compounds of the formula IB-8, preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by a cyclohexyl radical and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Of the compounds of the formula IA-9, preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by an aryl radical and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Of the compounds of the formula IB-9, preference is given to compounds of the formulae in which the skeleton is substituted on the left-hand side by a cyclohexyl radical and/or the skeleton is linked on the right-hand side to a cyclohexyl radical.

Of the compounds IA-10 and IB-10, preference is given to those containing one or more cyclohexyl rings. Particular preference is given here to compounds in which the cyclohexyl ring is linked directly to the skeleton.

Of the compounds IA-11, preference is given to those containing an unsubstituted or substituted 1,4-phenylene ring. Particular preference is given here to compounds in which the unsubstituted or substituted 1,4-phenylene ring is linked directly to the skeleton.

Of the compounds IB-11, preference is given to those containing one or more cyclohexyl rings. Particular preference is given here to compounds in which the cyclohexyl ring is linked directly to the skeleton.

Compounds of the formula I according to the invention may be chiral owing to their molecular structure and may accordingly occur in various enantiomeric forms. They can therefore be in racemic or optically active form.

The present invention also relates to liquid-crystal media which comprise one or more compound(s) of the formula I.

In a preferred embodiment, the liquid-crystal media in accordance with the present invention comprise

-   a) one or more dielectrically negative compound(s) of the formula I

-   -   in which the parameters have the meaning given above under         formula I,

-   b) one or more dielectrically negative compound(s) of the formula II

-   -   in which     -   R²¹ and R²² each, independently of one another, have the meaning         given above for R¹ under formula I,     -   Z²¹ and Z²² each, independently of one another, have the meaning         given above for Z¹ under formula I,     -   at least one of the rings

-   -    denotes

-   -    and the others, in each case independently of one another,         denote

-   -    preferably

-   -    particularly preferably

-   -    denotes

-   -    if present, denotes

-   -   L²¹ and L²² both denote C—F or one of the two denotes N and the         other denotes C—F, preferably both denote C—F, and     -   I denotes 0, 1 or 2, preferably 0 or 1;         and optionally

-   c) one or more dielectrically neutral compounds of the formula III

-   -   in which     -   R³¹ and R³² each, independently of one another, have the meaning         given above for R¹ under formula I, and     -   Z³¹, Z³² and Z³³ each, independently of one another, denote         —CH₂CH₂—, —CH═CH—, —COO— or a single bond,

-   -    each, independently of one another, denote

-   -   o and p, independently of one another, denote 0 or 1,     -   but preferably     -   R³¹ and R³² each, independently of one another, denote alkyl or         alkoxy having 1-5 C atoms or alkenyl having 2-5 C atoms,

-   -    each, independently of one another, denote

-   -   and very particularly preferably at least two of these rings         denote

-   -   in which very particularly preferably two adjacent rings are         linked directly, preferably

-   -   where one or more H atoms in the phenylene ring may be replaced,         independently of one another, by F or CN, preferably by F, and         one or two non-adjacent CH₂ groups of the cyclohexylene ring or         one of the cyclohexylene rings may be replaced by O atoms.

The liquid-crystal media preferably comprise one or more compounds of the formula I which contain no biphenyl unit.

The liquid-crystal media particularly preferably comprise one or more compounds of the formula I in which two adjacent rings are linked directly and preferably denote

where one or more H atoms in the phenylene ring may be replaced, independently of one another, by F or CN, preferably by F, and one or two non-adjacent CH₂ groups of the cyclohexylene ring or one of the cyclohexylene rings may be replaced by O atoms.

In a preferred embodiment, which may be identical with the embodiments just described, the liquid-crystal media comprise one or more compounds selected from the group of the compounds of the formula I-3.

The liquid-crystal medium preferably comprises one or more compounds selected from the group of the compounds of the formulae II-1 to II-3

in which R²¹, R²², Z¹², Z²²,

and I each have the meaning given above under formula II. Preferably, R²¹ is alkyl, preferably having 1-5 C atoms, R²¹ is alkyl or alkoxy, preferably each having 1 to 5 C atoms, and Z²² and Z²¹, if present, are a single bond.

The liquid-crystal medium particularly preferably comprises one or more compounds selected from the group of the compounds of the formulae III-1 to III-3:

in which R³¹, R³², Z³¹, Z³²,

and each have the meaning indicated above under formula III.

The liquid-crystal medium especially preferably comprises one or more compounds selected from the group of the compounds of the formulae III-1a to III-1d, III-1e, III-2a to III-2g, III-3a to III-3d and III-4-a:

in which n and m each, independently of one another, denote 1 to 5, and o and p each, independently both thereof and of one another, denote 0 to 3,

in which R³¹ and R³³ each have the meaning indicated above under formula III, preferably the meaning indicated under formula III-1, and the phenyl rings, in particular in the compounds III-2g and III-3c, may optionally be fluorinated, but not so that the compounds are identical with those of the formula II and the sub-formulae thereof. Preferably, R³¹ is n-alkyl having 1 to 5 C atoms, especially preferably having 1 to 3 C atoms, and R³² is n-alkyl or n-alkoxy having 1 to 5 C atoms or alkenyl having 2 to 5 C atoms. Of these, particular preference is given to compounds of the formulae III-1a to III-1d. Preferred fluorinated compounds of the formulae III-2g and III-3c are the compounds of the formulae III-2g′ and III-3c′

in which R³¹ and R³³ each have the meaning indicated above under formula III, preferably the meaning indicated under formula III-2g or III-3c.

In the present application, the term compounds is taken to mean both one compound and a plurality of compounds, unless expressly stated otherwise.

The liquid-crystal media according to the invention preferably have nematic phases of in each case from at least −20° C. to 80° C., preferably from −30° C. to 85° C. and very particularly preferably from −40° C. to 100° C. The term “have a nematic phase” here is taken to mean firstly that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and secondly also that no clearing occurs on heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the electro-optical application for at least 100 hours. At high temperatures, the clearing point is measured in capillaries by conventional methods.

Furthermore, the liquid-crystal media according to the invention are characterised by low optical anisotropy values.

The term “alkyl” preferably encompasses straight-chain and branched alkyl groups having 1 to 7 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2 to 5 carbon atoms are generally preferred.

The term “alkenyl” preferably encompasses straight-chain and branched alkenyl groups having 2 to 7 carbon atoms, in particular the straight-chain groups. Particularly preferred alkenyl groups are C₂- to C₇-1E-alkenyl, C₄- to C₇-3E-alkenyl, C₅— to C₇-4-alkenyl, C₆- to C₇₋₅-alkenyl and C₇₋₆-alkenyl, in particular C₂- to C₇-1E-alkenyl, C₄- to C₇-3E-alkenyl and C₅- to C₇-4-alkenyl. Examples of further preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The term “fluoroalkyl” preferably encompasses straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.

The term “oxaalkyl” or “alkoxyalkyl” preferably encompasses straight-chain radicals of the formula C_(n)H_(2n+1)—O—(CH₂)_(m), in which n and m each, independently of one another, denote 1 to 6. Preferably, n is 1 and m is 1 to 6.

Compounds containing a vinyl end group and compounds containing a methyl end group have low rotational viscosity.

In the present application, the term dielectrically positive compounds denotes compounds having a Δ∈ of >1.5, the term dielectrically neutral compounds denotes those in which −1.5≦Δ∈≦1.5, and the term dielectrically negative compounds denotes those having a Δ∈ of <−1.5. The dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of this mixture at 1 kHz in at least one test cell with a layer thickness of about 20 μm having a homeotropic surface alignment and at least one test cell with a layer thickness of about 20 μm having a homogeneous surface alignment. The measurement voltage is typically 0.5 V to 1.0 V, but is always less than the capacitive threshold of the respective liquid-crystal mixture.

The host mixture used for determining the applicationally relevant physical parameters is ZLI-4792 from Merck KGaA, Germany. As an exception, the determination of the dielectric anisotropy of dielectrically negative compounds is carried out using ZLI-2857, likewise from Merck KGaA, Germany. The values for the respective compound to be investigated are obtained from the change in the properties, for example the dielectric constants, of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed.

The concentration employed for the compound to be investigated is 10%. If the solubility of the compound to be investigated is inadequate for this purpose, the concentration employed is, by way of exception, halved, i.e. reduced to 5%, 2.5%, etc., until the concentration is below the solubility limit.

The term threshold voltage usually relates to the optical threshold for 10% relative contrast (V₁₀). In relation to the liquid-crystal mixtures of negative dielectric anisotropy, however, the term threshold voltage is used in the present application for the capacitive threshold voltage (V₀), also known as the Freedericks threshold, unless explicitly stated otherwise.

All concentrations in this application, unless explicitly stated otherwise, are indicated in percent by weight and relate to the corresponding mixture as a whole. All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, status November 1997, Merck KGaA, Germany, and apply to a temperature of 20° C., unless explicitly stated otherwise. An is determined at 589 nm and Δ∈ at 1 kHz.

In the case of the liquid-crystal media of negative dielectric anisotropy, the threshold voltage was determined as the capacitive threshold V₀ in cells with a liquid-crystal layer aligned homeotropically by means of lecithin.

The liquid-crystal media according to the invention may, if necessary, also comprise further additives and optionally also chiral dopants in the conventional amounts. The amount of these additives employed is in total 0% to 10%, based on the amount of the mixture as a whole, preferably 0.1% to 6%. The concentrations of the individual compounds employed are in each case preferably 0.1 to 3%. The concentration of these and similar additives is not taken into account when indicating the concentrations and the concentration ranges of the liquid-crystal compounds in the liquid-crystal media.

The compositions consist of a plurality of compounds, preferably 3 to 30, particularly preferably 6 to 20 and very particularly preferably 10 to 16 compounds, which are mixed in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, the completion of the dissolution process is particularly easy to observe. However, it is also possible to prepare the liquid-crystal mixtures in other conventional ways, for example using premixes or from a so-called “multibottle” system.

By means of suitable additives, the liquid-crystal phases according to the invention can be modified in such a way that they can be employed in any type of display and in particular of ECB displays and IPS displays that has been disclosed hitherto.

The examples below serve to illustrate the invention without limiting it. In the examples, the melting point T(C,N), the transition from the smectic (S) phase to the nematic (N) phase T(S,N) and the clearing point T(N,I) of a liquid-crystal substance are indicated in degrees Celsius. The various smectic phases are characterised by corresponding suffixes.

The percentages above and below are, unless explicitly stated otherwise, percent by weight, and the physical properties are the values at 20° C., unless explicitly stated otherwise.

All the temperature values indicated in this application are ° C., and all temperature differences are correspondingly differential degrees, unless explicitly stated otherwise.

In the present application and in particular in the synthesis examples and schemes, the abbreviations have the following meanings:

Bn benzyl,

cl.p. clearing point,

DEAD diethyl azodicarboxylate,

DIAD diisopropyl azodicarboxylate,

DMF dimethylformamide,

sat. saturated,

soln. solution,

MEM 2-methoxyethoxymethyl,

MOM methoxymethyl,

MTBE methyl tert-butyl ether,

Ph phenyl,

m.p. melting point,

SiO₂ silica gel,

TBS dimethyl-tert-butylsilyl,

THF tetrahydrofuran and

TMEDA tetramethylethylenediamine.

In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the trans-formation into chemical formulae taking place in accordance with Tables A and B below. All radicals C_(n)H_(2n+1) and C_(m)H_(2m+1) are straight-chain alkyl radicals having n and m C atoms respectively. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R¹, R², L¹, L² and L³:

Code for R¹, R², L¹, L², L³ R¹ R² L¹ L² L³ nm C_(n)H_(2n+1) C_(m)H_(2m+1) H H H nOm C_(n)H_(2n+1) OC_(m)H_(2m+1) H H H nO•m OC_(n)H_(2n+1) C_(m)H_(2m+1) H H H nmFF C_(n)H_(2n+1) C_(m)H_(2m+1) F H F nOmFF C_(n)H_(2n+1) OC_(m)H_(2m+1) F H F nO•mFF OC_(n)H_(2n+1) C_(m)H_(2m+1) F H F nO•OmFF OC_(n)H_(2n+1) OC_(m)H_(2m+1) F H F n C_(n)H_(2n+1) CN H H H nN•F C_(n)H_(2n+1) CN F H H nN•F•F C_(n)H_(2n+1) CN F F H nF C_(n)H_(2n+1) F H H H nF•F C_(n)H_(2n+1) F F H H nF•F•F C_(n)H_(2n+1) F F F H nCl C_(n)H_(2n+1) Cl H H H nCl•F C_(n)H_(2n+1) Cl F H H nCl•F•F C_(n)H_(2n+1) Cl F F H nmF C_(n)H_(2n+1) C_(m)H_(2m+1) F H H nCF₃ C_(n)H_(2n+1) CF₃ H H H nOCF₃ C_(n)H_(2n+1) OCF₃ H H H nOCF₃•F C_(n)H_(2n+1) OCF₃ F H H nOCF₃•F•F C_(n)H_(2n+1) OCF₃ F F H nOCF₂ C_(n)H_(2n+1) OCHF₂ H H H nOCF₂•F•F C_(n)H_(2n+1) OCHF₂ F F H nS C_(n)H_(2n+1) NCS H H H rVsN C_(r)H_(2r+1)—CH═CH—C_(s)H_(2s)— CN H H H nEsN C_(r)H_(2r+1)—O—C_(s)H_(2s)— CN H H H nAm C_(n)H_(2n+1) COOC_(m)H_(2m+1) H H H nF•Cl C_(n)H_(2n+1) F Cl H H

TABLE A

PYP

PYRP

BCH

CBC

CCH

CCP

CP

CPTP

CEPTP

D

ECCP

CECP

EPCH

HP

ME

PCH

PDX

PTP

BECH

EBCH

CPC

EHP

BEP

ET

TABLE B

CCZU-n-X (X = F, Cl, —OCF₃ = “OT”)

CDU-n-X (X = F, Cl, —OCF₃ = “OT”)

T3n

K3n

M3n

CGP-n-X (X = F, Cl, —OCF3 = “OT”)

CGU-n-X (X = F, Cl, —OCF₃ = “OT”)

CGG-n-X (X = F, Cl, —OCF₃ = “OT”)

Inm

CGU-n-X (X = F, Cl, —OCF₃ = “OT”)

C-nm

C15

CB15

CBC-nmF

CCN-nm

G3n

CCEPC-nm

CCPC-nm

CH-nm

HD-nm

HH-nm

NCB-nm

OS-nm

CHE

CBC-nmF

ECBC-nm

ECCH-nm

CCH-n1EM

T-nFN

GP-nO-X (X = F, Cl, —OCF3 = _(“)OT”)

CVCC-n-m

CVCP-n-m

CVCVC-n-m

CP-V-N

CC-n-V

CCG-V-F

CPP-nV2-m

CCP-V-m

CCP-V2-m

CPP-V-m

CPP-nV-m

CPP-V2-m

CC-V-V

CC-1V-V

CC-1V-V1

CC-2V-V

CC-2V-V2

CC-2V-V1

CC-V1-V

CC-V1-1V

CC-V2-1V

PCH-n(O)mFF

CCP-n(O)mFF

CPTP-n(O)mFF

Ph-n-(0)mFF

Ph-n0-(0)mFF

BHHO-n-(0)mFF

BHHO-n0-(0)mFF

BFFO-n-(0)mFF

BFFO-n0-(0)mFF

BFO-n-(0)mFF

BFO-n0-(0)mFF

BCOO-n-(0)mFF

BCOO-n0-(0)mFF

BHHO-O1P-n(O)-HFF

BHHO-O1P-n(O)-(O)mFF

BHHO-O1C-n(O)-(O)mFF

EXAMPLES

The following examples are intended to explain the invention without limiting it. Above and below, percentage data denote percent by weight. All temperatures are indicated in degrees Celsius. An denotes the optical anisotropy (589 nm, 20° C.), As the dielectric anisotropy (1 kHz, 20° C.), H.R. the voltage holding ratio (at 100° C., after 5 minutes in the oven, 1 V). V₁₀, V₅₀ and V₉₀ (the threshold voltage, mid-grey voltage and saturation voltage respectively) and V₀ (the capacitive threshold voltage) were each determined at 20° C.

Example 1 4,5-Difluoro-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]-chromene

1.1. Preparation of 1,2-difluoro-3-prop-2-ynyloxybenzene

115.0 g (0.88 mol) of 2,3-difluorophenol are refluxed for 3 h together with 118.2 ml (17.7 mol) of propargyl bromide (80% soln. in toluene) and 146.6 g (138.2 mol) of potassium carbonate in 1.6 l of ethyl methyl ketone. The batch is filtered, and the filter residue is washed with MTBE. The filtrate is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, n-heptane:MTBE=3:1).

1.2. Preparation of 7,8-difluoro-2H-chromene

73.0 g (0.43 mol) of 1,2-difluoro-3-prop-2-ynyloxybenzene are heated at 200° C. for 3 h in an autoclave together with 126.0 g (2.17 mol) of potassium fluoride in 650 ml of N,N-diethylaniline. Water is added to the batch, which is then acidified using 25% HCl. The solution is extracted with MTBE, and the combined organic phases are washed with sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, n-heptane:MTBE=10:1). The reaction does not proceed to completion, giving a mixture of 7,8-difluoro-2H-chromene and the starting material 1,2-difluoro-3-prop-2-ynyloxybenzene.

1.3. Preparation of 7,8-difluorochroman

A mixture of 7,8-difluoro-2H-chromene and 1,2-difluoro-3-prop-2-ynyloxybenzene (43.2 g) is hydrogenated at 20° C. for 1 h in 430 ml of THF in the presence of Pd/C (5% Pd). The batch is concentrated to dryness, and the crude product is purified by column chromatography (SiO₂, n-pentane:1-chlorobutane=4:1), giving pure 7,8-difluorochroman as a slightly yellowish liquid.

1.4. Preparation of 7,8-difluorochroman-6-ol

81.2 ml (0.13 mol) of n-BuLi (15% soln. in hexane) are added at −70° C. to a soln. of 20.0 g (0.12 mol) of 7,8-difluorochroman in 400 ml of THF. After 3 h at this temperature, 14.4 ml (0.13 mol) of trimethyl borate are added dropwise, and the batch is warmed to room temperature. 30 ml of dilute acetic acid (about 30%) are added, and 30 ml of aq. hydrogen peroxide soln. (35%) are carefully added to the batch. When the addition is complete, the mixture is stirred at 20° C. for 17 h. Water is added, and the batch is acidified using HCl. The solution is extracted a number of times with MTBE, and the combined organic phases are washed successively with water, sat. sodium chloride soln. and ammonium iron(II) sulfate soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, n-heptane:MTBE=2:1).

1.5. Preparation of 7,8-difluoro-6-methoxymethoxychroman

15.0 g (80.6 mmol) of 7,8-difluorochroman-6-ol are dissolved in 135 ml of dichloromethane, and 16.5 ml (94.2 mmol) of N-ethyldiisopropylamine are added with ice-cooling. After 5 min, 7.34 ml (97.0 mmol) of chloromethyl methyl ether are metered in the temperature range from 15 to 30° C. After 18 h at 20° C., 50 ml of triethylamine are added, and the batch is stirred again for 18 h. Water is added to the reaction mixture, and the organic phase is separated off. The aqueous phase is extracted with dichloromethane, and the combined organic phases are washed successively with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, n-heptane:MTBE=2:1), giving 7,8-difluoro-6-methoxymethoxychroman as a yellowish solid.

1.6. Preparation of 7,8-difluoro-5-iodo-6-methoxymethoxychroman

16.6 g (72.1 mmol) of 7,8-difluoro-6-methoxymethoxychroman are initially introduced in 350 ml of THF, and 54.3 ml (86.5 mmol) of n-BuLi (15% soln. in hexane) are added dropwise at −78° C. When the addition is complete, the mixture is stirred at this temperature for 30 min and subsequently at 20° C. for 1 h. The solution is re-cooled to −78° C., and a solution of 22.0 g (86.5 mol) of iodine in 100 ml of THF is added dropwise. The reaction mixture is stirred at room temperature for 1.5 h and subsequently diluted with MTBE. The solution is washed with water and sat. sodium chloride soln. and dried using sodium sulfate. The crude product remaining after removal of the solvents is purified by column chromatography (SiO₂, n-heptane:MTBE=2:1), giving 7,8-difluoro-5-iodo-6-methoxymethoxychroman as a brownish oil.

1.7. Preparation of 7,8-difluoro-5-iodochroman-6-ol

10.4 ml of conc. HCl are added to a solution of 20.2 g (56.7 mmol) of 7,8-difluoro-5-iodo-6-methoxymethoxychroman in 100 ml of THF, and the mixture is stirred at 20° C. for 18 h. The batch is diluted with MTBE, and the solution is washed with water. The aqueous phase is extracted with MTBE, and the combined organic phases are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, n-heptane:MTBE=1:1), giving 7,8-difluoro-5-iodochroman-6-ol as a pale-brown solid.

1.8. Preparation of 7,8-difluoro-5-(4-propylcyclohexylethynyl)chroman-6-ol

7.0 g (22.4 mmol) of 7,8-difluoro-5-chroman-6-ol are stirred at 50° C. for 18 h together with 5.06 g (33.5 mmol) of 1-ethynyl-4-propylcyclohexane in the presence of 472 mg (0.67 mmol) of bis(triphenylphosphine)palladium(II) chloride and 128 mg (0.67 mmol) of copper(I) iodide in 90 ml of triethylamine. After cooling, the batch is added to ice/water and acidified using hydrochloric acid. The mixture is extracted a number of times with MTBE, and the combined extracts are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, 1-chlorobutane). The oil obtained is used directly for the following reaction.

1.9. Preparation of 4,5-difluoro-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo-[3,2-f]chromene

5.80 g (17.3 mmol) of 7,8-difluoro-5-(4-propylcyclohexylethynyl)chroman-6-ol are initially introduced together with 0.26 ml (1.73 mmol) of TMEDA, and 9.6 ml (9.6 mmol) of diethylzinc (1 M soln. in heptane) are added to the mixture at 3° C. When the evolution of gas has subsided, 25 ml of toluene are added, and the batch is refluxed for 40 h. The solution is added to sat. ammonium chloride soln., and the mixture is extracted with toluene. The combined organic phases are washed with water and sat. sodium chloride soln. and dried using sodium sulfate. The solution is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, 1-chlorobutane:pentane=2:1). Further purification is carried out by repeated recrystallisation from ethanol at reduced temperature, giving 4,5-difluoro-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]chromene as a colourless solid having a melting point of 89° C. (Δ∈=−5.0).

¹H-NMR (300 MHz, CHCl₃): δ=6.23 (dd, 1H, J=3.0 Hz, J=1.0 Hz, 1-H), 4.27-4.24 (m, 2H, 7-H), 2.81 (td, 2H, J=7.8 Hz, J=1.5 Hz, 9-H), 2.67 (tm, 1H, J=12.0 Hz, H_(aliph.)), 2.18-2.04 (m, 4H, H_(aliph.)), 1.87 (dm, 2H, J=12.0 Hz, H_(aliph.)), 1.54-1.43 (m, 2H, H_(aliph.)), 1.39-1.27 (m, 3H, H_(aliph.)), 1.26-1.27 (m, 2H, H_(aliph.)), 1.11-0.97 (m, 2H, H_(aliph.)), 0.90 (t, 3H, J=7.1 Hz, CH₂CH₂CH₃).

¹⁹F-NMR (282 MHz, CHCl₃): δ=−162.7 (dm, 1F, J=19.5 Hz), −166.5 (d, 1F, J=19.5 Hz).

MS (EI): m/e (%)=334 (100, M⁺), 249 (48).

Example 2 4,5-Difluoro-2-(4-propylcyclohexyl)-1,7,8,9-tetrahydro-2H-furo-[3,2-f]chromene

2.1. Preparation of 4,5-difluoro-2-(4-propylcyclohexyl)-1,7,8,9-tetrahydro-2H-furo[3,2-f]chromene

1.00 g (2.99 mmol) of 4,5-difluoro-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]chromene is hydrogenated for 15 h at room temperature and atmospheric pressure in THF using elemental hydrogen in the presence of Pd/C (5% Pd). The reaction soln. is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, 1-chlorobutane pentane=2:1). Further purification is carried out by recrystallisation from ethanol, giving 4,5-difluoro-2-(4-propylcyclohexyl)-1,7,8,9-tetrahydro-2H-furo[3,2-f]chromene as a colourless solid having an m.p. of 96° C. (Δ∈=−7.0).

¹H-NMR (300 MHz, CHCl₃): δ=4.61-4.53 (m, 1H, 2-H), 4.19-4.16 (m, 2H, 7-H), 3.04-2.96 (m, 1H, 1-H), 2.84-2.75 (m, 1H, 1-H), 2.60-2.54 (m, 2H, 9-H), 2.05-1.97 (m, 3H, H_(aliph.)), 1.81 (dm, 2H, J=13.2 Hz, H_(aliph.)), 1.75-1.66 (m, 2H, H_(aliph.)), 1.64-1.56 (m, 1H, H_(aliph.)), 1.38-1.24 (m, 2H, H_(aliph.)), 1.22-1.01 (m, 4H, H_(aliph.)), 0.98-0.82 (m, 5H, H_(aliph.)).

¹⁹F-NMR (282 MHz, CHCl₃): δ=−162.1 (d, 1F, J=19.5 Hz), −163.1 (d, 1F, J=19.5 Hz).

MS (EI): m/e (%)=336 (82, M⁺), 199 (100).

Example 3 4,5-Difluoro-7-pentyl-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]chromene

3.1. Preparation of 1-(1-ethynylhexyloxy)-2,3-difluorobenzene

42.4 g (0.33 mol) of 2,3-difluorophenol are initially introduced in 1.2 l of THF together with 50.0 ml (0.34 mol) of 1-octyn-3-ol and 94.1 g (0.36 mol) of triphenylphosphine, and a solution of 76.1 ml (0.39 mol) of DIAD in 100 ml of THF is added dropwise. After 19 h at 20° C., the mixture is diluted with MTBE, and the batch is washed with water. The aqueous phase is extracted with MTBE, and the combined organic phases are washed with sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, 1-chlorobutane), giving 1-(1-ethynylhexyloxy)-2,3-difluorobenzene as a colourless oil.

3.2. Preparation of 7,8-difluoro-2-pentyl-2H-chromene

62.0 g (0.26 mol) of 1-(1-ethynylhexyloxy)-2,3-difluorobenzene are heated at 195° C. for 2 h in 390 ml of N,N-diethylaniline. The batch is diluted with MTBE and washed a number of times with 1 N HCl. The organic phase is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, n-pentane:1-chlorobutane=5:1), giving 7,8-difluoro-2-pentyl-2H-chromene as a brown oil.

3.3. Preparation of 7,8-difluoro-2-pentylchroman

51.0 g (0.21 mol) of 7,8-difluoro-2-pentyl-2H-chromene are hydrogenated for 1 h at room temperature in 510 ml of toluene in the presence of Pd/C (5% Pd). The batch is concentrated to dryness. The crude product (yellowish liquid) can be used directly for the next step.

3.4. Preparation of 7,8-difluoro-2-pentylchroman-6-ol

52.4 g (about 0.22 mol) of crude 7,8-difluoro-2-pentylchroman are initially introduced in 400 ml of THF, and 150.7 ml (0.24 mol) of n-BuLi (15% soln. in hexane) are added at −70° C. After 3 h at this temperature, 26.8 ml (0.24 mol) of trimethyl borate are added dropwise, and the batch is warmed to room temperature. 55 ml of dilute acetic acid (about 30%) are added, and 57 ml of hydrogen peroxide soln. (35%) are carefully added to the batch. When the addition is complete, the mixture is stirred for 17 h at room temperature. Water is added, and the batch is acidified using HCl. The solution is extracted a number of times with MTBE, and the combined organic phases are washed successively with water, sat. sodium chloride soln. and ammonium iron(II) sulfate soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, n-heptane:MTBE=2:1).

3.5. Preparation of 7,8-difluoro-6-methoxymethoxy-2-pentylchroman

16.9 g (65.9 mmol) of 7,8-difluoro-2-pentylchroman-6-ol are dissolved in 110 ml of dichloromethane, and 13.5 ml (77.1 mmol) of N-ethyldiisopropylamine are added with ice-cooling. After 5 min, 6.0 ml (79.0 mmol) of chloromethyl methyl ether are metered in the temperature range from 15 to 30° C. After 16 h at room temperature, 50 ml of triethylamine are added, and the batch is stirred again for 24 h. Water is added to the reaction mixture, and the organic phase is separated off. The aqueous phase is extracted with dichloromethane, and the combined organic phases are washed successively with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, 1-chlorobutane), giving 7,8-difluoro-6-methoxymethoxy-2-pentylchroman as a yellowish oil.

3.6. Preparation of 7,8-difluoro-5-iodo-6-methoxymethoxy-2-pentylchroman

17.7 g (58.9 mmol) of 7,8-difluoro-6-methoxymethoxy-2-pentylchroman are initially introduced in 370 ml of THF, and 47.7 ml (75.9 mmol) of n-BuLi (15% soln. in hexane) are added dropwise at −78° C. When the addition is complete, the mixture is stirred at this temperature for 30 min and subsequently at room temperature for 1 h. The solution is re-cooled to −78° C., and a solution of 17.9 g (70.7 mol) of iodine in 100 ml of THF is added dropwise. The reaction mixture is stirred at room temperature for 90 min and subsequently diluted with MTBE. Sat. sodium hydrogensulfite soln. is added to the mixture, which is subsequently washed with water and sat. sodium chloride soln. The crude product remaining after drying using sodium sulfate and removal of the solvents is purified by column chromatography (SiO₂, n-heptane:MTBE=3:1), giving 7,8-difluoro-5-iodo-6-methoxymethoxy-2-pentylchroman as a brown oil.

3.7. Preparation of 7,8-difluoro-5-iodo-2-pentylchroman-6-ol

9.2 ml of conc. HCl are added to a solution of 21.4 g (50.2 mmol) of 7,8-difluoro-5-iodo-6-methoxymethoxy-2-pentylchroman in 90 ml of THF, and the mixture is stirred at room temperature for 17 h. The batch is diluted with MTBE, and the solution is washed with water. The aqueous phase is extracted with MTBE, and the combined organic phases are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, n-heptane:MTBE=1:1), giving 7,8-difluoro-5-iodo-2-pentylchroman-6-ol as a beige solid.

3.8. Preparation of 7,8-difluoro-2-pentyl-5-(4-propylcyclohexylethynyl)chroman-6-ol

8.0 g (20.9 mmol) of 7,8-difluoro-5-iodo-2-pentylchroman-6-ol are stirred at 50° C. for 19 h together with 4.72 g (31.4 mmol) of 1-ethynyl-4-propylcyclohexane in the presence of 441 mg (0.63 mmol) of bis(triphenylphosphine)palladium(II) chloride and 120 mg (0.63 mmol) of copper(I) iodide in 90 ml of triethylamine. After cooling, the batch is added to ice/water and acidified using hydrochloric acid. The mixture is extracted a number of times with MTBE, and the combined extracts are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, 1-chlorobutane). The phenol obtained is used directly for the following reaction.

3.9. Preparation of 4,5-difluoro-7-pentyl-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]chromene

3.00 g (7.41 mmol) of 7,8-difluoro-2-pentyl-5-(4-propylcyclohexylethynyl)chroman-6-ol are initially introduced together with 0.11 ml (0.74 mmol) of TMEDA, and 4.1 ml (4.1 mmol) of diethylzinc (1 M soln. in heptane) are added to the mixture at 3° C. When the evolution of gas has subsided, 11 ml of toluene are added, and the batch is refluxed for 40 h. The solution is added to sat. ammonium chloride soln., and the mixture is extracted with toluene. The combined organic phases are washed with water and sat. sodium chloride soln. and dried using sodium sulfate. The solution is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, 1-chlorobutane:pentane=2:1). Further purification is carried out by repeated recrystallisation from ethanol at reduced temperature, giving 4,5-difluoro-7-pentyl-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]chromene as a colourless solid having the phase sequence C 56° C. N 62° C. I (Δ∈=−6.8).

¹H-NMR (400 MHz, CHCl₃): δ=6.22 (dd, 1H, J=3.2 Hz, J=0.8 Hz, 1-H), 4.05-3.99 (m, 1H, 7-H), 2.83-2.79 (m, 2H, 9-H), 2.67 (tm, 1H, J=12.0 Hz, H_(aliph.)), 2.17-2.04 (m, 3H, H_(aliph.)), 1.90-1.75 (m, 4H, H_(aliph.)), 1.67-1.53 (m, 4H, H_(aliph.)), 1.50-1.40 (m, 2H, H_(aliph.)), 1.38-1.26 (m, 6H, H_(aliph.)), 1.25-1.18 (m, 2H, H_(aliph.)), 1.09-0.99 (m, 2H, H_(aliph.)), 0.93-0.88 (m, 6H, CH₂CH₃).

¹⁹F-NMR (376 MHz, CHCl₃): δ=−162.9 (dm, 1F, J=19.2 Hz), −166.2 (d, 1F, J=19.2 Hz).

MS (EI): m/e (%)=404 (98, M⁺), 307 (100).

Example 4 4,5-Difluoro-7-pentyl-2-(4-propylcyclohexyl)-1,7,8,9-tetrahydro-2H-furo[3,2-f]chromene

4.1. Preparation of 4,5-difluoro-7-pentyl-2-(4-propylcyclohexyl)-1,7,8,9-tetrahydro-2H-furo[3,2-f]chromene

1.00 g (2.46 mmol) of 4,5-difluoro-7-pentyl-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]chromene is hydrogenated for 19 h at room temperature and atmospheric pressure in THF using elemental hydrogen in the presence of Pd/C (5% Pd). The reaction soln. is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, 1-chlorobutane:pentane=2:1). Further purification is carried out by recrystallisation from ethanol, giving 4,5-difluoro-7-pentyl-2-(4-propylcyclohexyl)-8,9-dihydro-7H-furo[3,2-f]chromene as a colourless solid having an m.p. of 101° C. (Δ∈=−10.5).

¹H-NMR (300 MHz, CHCl₃): δ=4.61-4.52 (m, 1H, 2-H), 3.97-3.88 (m, 1H, 7-H), 3.04-2.94 (m, 1H, 1-H), 2.84-2.74 (m, 1H, 1-H), 2.67-2.47 (m, 2H, 9-H), 2.05-1.96 (m, 2H, H_(aliph.)), 1.85-1.66 (m, 4H, H_(aliph.)), 1.65-1.41 (m, 3H, H_(aliph.)), 1.39-1.26 (m, 5H, H_(aliph.)), 1.24-1.01 (m, 4H, H_(aliph.)), 0.98-0.82 (m, 5H, H_(aliph.)).

¹⁹F-NMR (282 MHz, CHCl₃): δ=−161.9 (dm, 1F, J=19.2 Hz), −163.8 (d, 1F, J=19.2 Hz).

MS (EI): m/e (%)=406 (100, M⁺).

Example 5 4,5-Difluoro-2-methyl-7-propyl-8,9-dihydro-7H-furo[3,2-f]-chromene

5.1. Preparation of 5-bromo-1,2-difluoro-3-prop-2-ynyloxybenzene

50.0 g (0.24 mol) of 5-bromo-2,3-difluorophenol are refluxed for 3 h together with 32.0 ml (0.29 mol) of propargyl bromide (80% soln. in toluene) and 39.7 g (0.29 mol) of potassium carbonate in 860 ml of ethyl methyl ketone. The batch is filtered, and the filter residue is washed with MTBE. The filtrate is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, n-heptane:MTBE=3:1).

5.2. Preparation of 4-bromo-6,7-difluoro-2-methylbenzofuran

51.9 g (0.21 mol) of 5-bromo-1,2-difluoro-3-prop-2-ynyloxybenzene are heated at 205° C. for 4 h together with 20.7 g (0.14 mol) of caesium fluoride in 300 ml of N,N-diethylaniline. The batch is diluted with MTBE and washed a number of times with 1 N HCl. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, n-heptane:1-chlorobutane=3:1), giving 4-bromo-6,7-difluoro-2-methylbenzofuran as a yellow solid.

5.3. Preparation of 4-bromo-6,7-difluoro-2-methylbenzofuran-5-ol

107.1 ml (0.17 mol) of n-BuLi (15% soln. in hexane) are initially introduced at −70° C. in 150 ml of THF, and 29.0 ml (0.17 mol) of 2,2,6,6-tetramethylpiperidine are added. After 30 min at this temperature, a solution of 38.3 g (0.16 mol) of 4-bromo-6,7-difluoro-2-methylbenzofuran in 100 ml of THF is metered in. After 3 h at this temperature, 19.1 ml (0.17 mol) of trimethyl borate are added dropwise, and the batch is warmed to room temperature. 40 ml of dilute acetic acid (about 30%) are added, and 40 ml of aqueous hydrogen peroxide soln. (35%) are carefully added to the batch. When the addition is complete, the mixture is stirred at 20° C. for 18 h. Water is added, and the batch is acidified using HCl. The solution is extracted a number of times with MTBE, and the combined organic phases are washed successively with water, sat. sodium chloride soln. and ammonium iron(II) sulfate soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, n-heptane:1-chlorobutane=2:1), giving 4-bromo-6,7-difluoro-2-methylbenzofuran-5-ol as a beige solid.

5.4. Preparation of 4-bromo-6,7-difluoro-5-(2-methoxyethoxymethoxy)-2-methylbenzofuran

23.0 g (87.4 mmol) of 4-bromo-6,7-difluoro-2-methylbenzofuran-5-ol are initially introduced at 0° C. in 120 ml of dichloromethane, and 17.9 ml (0.11 mol) of N-ethyldiisopropylamine and 11.9 ml (0.11 mol) of MEMCI are added successively. The batch is stirred at 20° C. for 16 h, and excess MEMCI is quenched using triethylamine. Water is added, and the organic phase is separated off. The aqueous phase is extracted with dichloromethane, and the combined organic phases are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, n-heptane:MTBE=2:1).

5.5. Preparation of 6,7-difluoro-5-(2-methoxyethoxymethoxy)-2-methylbenzofuran-4-carbaldehyde

27.2 g (77.5 mmol) of 4-bromo-6,7-difluoro-5-(2-methoxyethoxymethoxy)-2-methylbenzofuran are initially introduced at −75° C. in 500 ml of THF, and 52.0 ml (85.2 mmol) of n-BuLi (15% soln. in hexane) are added. After 2 h at this temperature, 15.5 ml (155 mmol) of N-formylmorpholine are metered in, and the batch is stirred at this temperature for 2 h. The reaction soln. is slowly warmed to −10° C. and hydrolysed using dil. HCl. The batch is extracted with MTBE, and the combined organic phases are washed with sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, n-heptane:MTBE=2:1→n-heptane:MTBE=1:1).

5.6. Preparation of 6,7-difluoro-5-hydroxy-2-methylbenzofuran-4-carbaldehyde

18.0 g (60.0 mmol) of 6,7-difluoro-5-(2-methoxyethoxymethoxy)-2-methylbenzofuran-4-carbaldehyde are stirred for 17 h at 20° C. together with 11.0 ml of conc. HCl in 100 ml of THF. The reaction soln. is diluted with MTBE and washed with water. The aqueous phase is extracted with MTBE, and the combined organic phases are washed successively with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (SiO₂, 1-chlorobutane), giving 6,7-difluoro-5-hydroxy-2-methylbenzofuran-4-carbaldehyde as a yellow crystalline solid.

5.7. Preparation of 4,5-difluoro-2-methyl-7-propyl-7H-furo[3,2-f]chromene

4.0 g (18.9 mmol) of 6,7-difluoro-5-hydroxy-2-methylbenzofuran-4-carbaldehyde are stirred for 20 h at 90° C. together with 2.79 g (24.5 mmol) of 1-penteneboronic acid and 0.72 ml (3.73 mmol) of dibenzylamine in 95 ml of 1,4-dioxane. Water is added to the reaction mixture, which is then extracted with MTBE. The organic phase is separated off, and the aqueous phase is extracted with MTBE. The combined organic phases are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is firstly purified by column chromatography (SiO₂, 1-chlorobutane) and subsequently crystallised from methanol, giving 4,5-difluoro-2-methyl-7-propyl-7H-furo[3,2-f]chromene as a yellow, crystalline solid.

5.8. Preparation of 4,5-difluoro-2-methyl-7-propyl-8,9-dihydro-7H-furo[3,2-f]-chromene

3.5 g (13.2 mmol) of 4,5-difluoro-2-methyl-7-propyl-7H-furo[3,2-f]chromene are hydrogenated for a few minutes in toluene using elemental hydrogen in the presence of Pd/C (5% Pd). The reaction soln. is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, n-heptane:1-chlorobutane=2:1). The further purification is carried out by recrystallisation from ethanol and subsequent absorptive (SiO₂, n-heptane:1-chlorobutane=3:1) filtration, giving 4,5-difluoro-2-methyl-7-propyl-8,9-dihydro-7H-furo[3,2-f]chromene as a colourless solid having an m.p. of 75° C. (Δ∈c=−7.8).

¹H-NMR (250 MHz, CHCl₃): δ=6.26 (q, 1H, ⁴J=1.0 Hz, 1-H), 4.09-4.00 (m, 1H, 7-H), 2.83-2.77 (m, 2-H, 9-H), 2.43 (s, 3H, 2-Me), 2.12-2.02 (m, 1H, 8-H), 1.86-1.70 (m, 2H, H_(aliph.)), 1.69-1.45 (m, 3H, 8-H, H_(aliph.)), 0.99 (t, 3H, CH₂CH₂CH₃).

¹⁹F-NMR (235 MHz, CHCl₃): δ=−164.2 (dm, 1F, J=19.5 Hz), −167.4 (d, 1F, J=19.5 Hz).

MS (EI): m/e (%)=266 (37, M⁺), 223 (6, [M-C₃H₇]⁺), 197 (100).

Example 6 4,5-Difluoro-2-methyl-7-propyl-1,7,8,9-tetrahydro-2H-furo[3,2-f]-chromene

6.1. Preparation of 4,5-difluoro-2-methyl-7-propyl-1,7,8,9-tetrahydro-2H-furo-[3,2-f]chromene

2.0 g (7.51 mmol) of 4,5-difluoro-2-methyl-7-propyl-8,9-dihydro-7H-furo-[3,2-f]chromene are hydrogenated for 18 h at elevated temperature in THF using elemental hydrogen in the presence of Pd/C (5% Pd). The reaction soln. is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, 1-chlorobutane), giving 4,5-difluoro-2-methyl-7-propyl-1,7,8,9-tetrahydro-2H-furo[3,2-f]chromene as a colourless solid having an m.p. of 87° C. (Δ∈=−10.1).

¹H-NMR (250 MHz, CHCl₃): δ=5.06-4.92 (m, 1H, 2-H), 4.00-3.90 (m, 1H, 7-H), 3.21-3.09 (m, 1H, 1-H), 2.71-2.46 (m, 3H, 1-H, 9-H), 2.06-1.95 (m, 1H, 8-H), 1.80-1.53 (m, 5H, 8-H, CH₂CH₂CH₃), 1.48 (d, 3H, J=6.3 Hz, 2-Me), 0.97 (t, 3H, J=7.0 Hz, CH₂CH₂CH₃).

¹⁹F-NMR (235 MHz, CHCl₃): δ=−160.6 (dm, 1F, J=19.5 Hz), −162.8 (d, 1F, J=19.5 Hz).

MS (EI): m/e (%)=268 (89, M⁺), 225 (6, [M-C₃H₇]⁺), 199 (100).

Example 7 4,5-Difluoro-2-methyl-7-pentyl-8,9-dihydro-7H-furo[3,2-f]-chromene

7.1. Preparation of 4,5-difluoro-2-methyl-7-pentyl-7H-furo[3,2-f]chromene

4.0 g (18.6 mmol) of 6,7-difluoro-5-hydroxy-2-methylbenzofuran-4-carbaldehyde are stirred for 20 h at 90° C. together with 3.21 g (22.6 mmol) of 1-hepteneboronic acid and 0.72 ml (3.73 mmol) of dibenzylamine in 95 ml of 1,4-dioxane. Water is added to the reaction mixture, which is then extracted with MTBE. The organic phase is separated off, and the aqueous phase is extracted with MTBE. The combined organic phases are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is firstly purified by column chromatography (SiO₂, 1-chlorobutane) and subsequently crystallised from methanol, giving 4,5-difluoro-2-methyl-7-pentyl-7H-furo[3,2-f]chromene as a yellow, crystalline solid.

7.2. Preparation of 4,5-difluoro-2-methyl-7-pentyl-8,9-dihydro-7H-furo[3,2-f]-chromene

2.8 g (9.58 mmol) of 4,5-difluoro-2-methyl-7-pentyl-7H-furo[3,2-f]chromene are hydrogenated for a few minutes in toluene using elemental hydrogen in the presence of Pd/C (5% Pd). The reaction soln. is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, n-heptane:1-chlorobutane=2:1). The further purification is carried out by recrystallisation from ethanol, giving 4,5-difluoro-2-methyl-7-pentyl-8,9-dihydro-7H-furo[3,2-f]chromene as a colourless solid having an m.p. of 61° C.

¹H-NMR (500 MHz, CHCl₃): δ=6.27 (bs, 1H, 1-H), 4.06-4.01 (m, 1H, 7-H), 2.82-2.79 (m, 2H, 9-H), 2.44 (s, 3H, 2-Me), 2.10-2.05 (m, 1H, H_(aliph.)), 1.86-1.75 (m, 2H, H_(aliph.)), 1.67-1.60 (m, 1H, H_(aliph.)), 1.59-1.54 (m, 1H, H_(aliph.)), 1.51-1.43 (m, 1H, H_(aliph.)), 1.37-1.33 (m, 4H, H_(aliph.)), 0.91 (t, 3H, J=7.0 Hz, (CH₂)₄CH₃).

¹⁹F-NMR (235 MHz, CHCl₃): δ=−163.2 (dm, 1F, J=19.5 Hz), −166.4 (d, 1F, J=19.5 Hz).

MS (EI): m/e (%)=294 (27, M⁺), 223 (6, [M-C₅H₁₁]⁺), 197 (100).

Example 8 4,5-Difluoro-2-methyl-7-pentyl-1,7,8,9-tetrahydro-2H-furo[3,2-f]-chromene

8.1. Preparation of 4,5-difluoro-2-methyl-7-pentyl-1,7,8,9-tetrahydro-2H-furo-[3,2-f]chromene

2.0 g (7.51 mmol) of 4,5-difluoro-2-methyl-7-pentyl-8,9-dihydro-7H-furo-[3,2-f]chromene are hydrogenated for 18 h at elevated temperature in THF using elemental hydrogen in the presence of Pd/C (5% Pd). The reaction soln. is concentrated to dryness, and the residue is purified by column chromatography (SiO₂, n-heptane:MTBE=4:1). Further purification is carried out by recrystallisation from ethanol at 5° C., giving 4,5-difluoro-2-methyl-7-pentyl-1,7,8,9-tetrahydro-2H-furo[3,2-f]chromene as a colourless solid having an m.p. of 76° C. (Δ∈=−8.2).

¹H-NMR (250 MHz, CHCl₃): δ=5.07-4.92 (m, 1H, 2-H), 3.99-3.88 (m, 1H, 7-H), 3.22-3.09 (m, 1H, 1-H), 2.71-2.53 (m, 3H, 1-H, 9-H), 2.06-1.96 (m, 1H, 8-H), 1.80-1.51 (m, 5H, H_(aliph.)), 1.48 (d, 3H, J=6.3 Hz, 2-Me), 1.36-1.32 (m, 4H, H_(aliph.)), 0.91 (t, 3H, J=7.0 Hz, (CH₂)₄CH₃).

¹⁹F-NMR (235 MHz, CHCl₃): δ=−162.1 (dm, 1F, J=19.5 Hz), −164.2 (d, 1F, J=19.5 Hz).

MS (EI): m/e (%)=296 (98, M⁺), 199 (100).

Example 9 4,5-Difluoro-7-pentyl-2-(4-propylphenyl)-8,9-dihydro-7H-furo-[3,2-f]chromene

9.1. Preparation of 4,5-difluoro-7-pentyl-2-(4-propylphenyl)-8,9-dihydro-7H-furo[3,2-f]chromene

2.0 g (5.23 mmol) of 7,8-difluoro-5-iodo-2-pentylchroman-6-ol are firstly stirred for 6 h at 60° C. together with 1.13 g (7.85 mmol) of ethynyl-n-propylbenzene in the presence of 110 mg (0.16 mmol) of bis(triphenylphosphine)palladium(II) chloride and 30 mg (0.16 mmol) of copper(I) iodide in 22 ml of triethylamine. The mixture is subsequently refluxed for 18 h. After cooling, the batch is added to ice/water and acidified using hydrochloric acid. The mixture is extracted a number of times with MTBE, and the combined extracts are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO₂, pentane: 1-chlorobutane=10:1). Further purification is carried out by recrystallisation from ethanol at 5° C., giving 4,5-difluoro-7-pentyl-2-(4-propylphenyl)-8,9-dihydro-7H-furo[3,2-f]chromene as a solid having the phase sequence Tg −31° C. C 70° C. N 79° C. I (Δ∈=−7.2).

¹H-NMR (250 MHz, CHCl₃): δ=7.72 (d, 2H, J=8.3 Hz, H_(arom.)), 7.23 (d, 2H, J=8.3 Hz, H_(arom.)), 6.81 (d, 1H, J=2.7 Hz), 4.08-4.00 (m, 1H, 7-H), 2.88-2.83 (m, 2H, 9-H), 2.62 (t, 2H, J=7.8 Hz, H_(benzyl.)), 2.14-2.05 (m, 1H, H_(aliph.)), 1.90-1.76 (m, 2H, H_(aliph.)), 1.73-1.61 (m, 4H, H_(aliph.)), 1.57-1.44 (m, 1H, H_(aliph.)), 1.39-1.33 (m, 4H, H_(aliph.)), 0.98-0.89 (m, 6H, H_(aliph.)).

¹⁹F-NMR (282 MHz, CHCl₃): δ=−162.5 (dd, 1F, J=19.2 Hz, J=1.9 Hz), −164.3 (d, 1F, J=19.2 Hz).

MS (EI): m/e (%)=398 (100, M⁺), 301 (97).

Examples 10 to 86

The following are prepared analogously to Examples 1, 3 and 9:

Phase sequence No. R¹ R² T/° C. 10 CH₃ CH₃ 11 CH₃ C₂H₅ 12 CH₃ n-C₃H₇ 13 CH₃ n-C₄H₉ 15 CH₃ n-C₅H₁₁ 16 CH₃ n-C₆H₁₃ 17 CH₃ n-C₇H₁₅ 18 C₂H₅ CH₃ 19 C₂H₅ C₂H₅ 20 C₂H₅ n-C₃H₇ 21 C₂H₅ n-C₄H₉ 22 C₂H₅ n-C₅H₁₁ 23 C₂H₅ n-C₆H₁₃ 24 C₂H₅ n-C₇H₁₅ 25 n-C₃H₇ CH₃ 26 n-C₃H₇ C₂H₅ 27 n-C₃H₇ n-C₃H₇ 28 n-C₃H₇ n-C₄H₉ 3 n-C₃H₇ n-C₅H₁₁ C 56 N 62 I 29 n-C₃H₇ n-C₆H₁₃ 30 n-C₃H₇ n-C₇H₁₅ 31 n-C₄H₉ CH₃ 32 n-C₄H₉ C₂H₅ 33 n-C₄H₉ n-C₃H₇ 34 n-C₄H₉ n-C₄H₉ 35 n-C₄H₉ n-C₅H₁₁ 36 n-C₄H₉ n-C₆H₁₃ 37 n-C₄H₉ n-C₇H₁₅ 38 n-C₅H₁₁ CH₃ 39 n-C₅H₁₁ C₂H₅ 40 n-C₅H₁₁ n-C₃H₇ 41 n-C₅H₁₁ n-C₄H₉ 42 n-C₅H₁₁ n-C₅H₁₁ 43 n-C₅H₁₁ n-C₆H₁₃ 44 n-C₅H₁₁ n-C₇H₁₅ 45 n-C₆H₁₃ CH₃ 46 n-C₆H₁₃ C₂H₅ 47 n-C₆H₁₃ n-C₃H₇ 48 n-C₆H₁₃ n-C₄H₉ 49 n-C₆H₁₃ n-C₅H₁₁ 50 n-C₆H₁₃ n-C₆H₁₃ 51 n-C₆H₁₃ n-C₇H₁₅ 52 n-C₇H₁₅ CH₃ 53 n-C₇H₁₅ C₂H₅ 54 n-C₇H₁₅ n-C₃H₇ 55 n-C₇H₁₅ n-C₄H₉ 56 n-C₇H₁₅ n-C₅H₁₁ 57 n-C₇H₁₅ n-C₆H₁₃ 58 n-C₇H₁₅ n-C₇H₁₅ 59 CH₃O CH₃ 60 CH₃O C₂H₅ 61 CH₃O n-C₃H₇ 62 CH₃O n-C₄H₉ 63 CH₃O n-C₅H₁₁ 64 CH₃O n-C₆H₁₃ 65 CH₃O n-C₇H₁₅ 66 C₂H₅O CH₃ 67 C₂H₅O C₂H₅ 68 C₂H₅O n-C₃H₇ 69 C₂H₅O n-C₄H₉ 70 C₂H₅O n-C₅H₁₁ 71 C₂H₅O n-C₆H₁₃ 72 C₂H₅O n-C₇H₁₅ 73 CH₂═CH CH₃ 74 CH₂═CH C₂H₅ 75 CH₂═CH n-C₃H₇ 76 CH₂═CH n-C₄H₉ 77 CH₂═CH n-C₅H₁₁ 78 CH₂═CH n-C₆H₁₃ 79 CH₂═CH n-C₇H₁₅ 80 CH₃—CH═CH CH₃ 81 CH₃—CH═CH C₂H₅ 82 CH₃—CH═CH n-C₃H₇ 83 CH₃—CH═CH n-C₄H₉ 84 CH₃—CH═CH n-C₅H₁₁ 85 CH₃—CH═CH n-C₆H₁₃ 86 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 87 to 163

The following are prepared analogously to Examples 1, 3 and 9:

Phase sequence No. R¹ R² T/° C. 87 CH₃ CH₃ 88 CH₃ C₂H₅ 89 CH₃ n-C₃H₇ 90 CH₃ n-C₄H₉ 91 CH₃ n-C₅H₁₁ 92 CH₃ n-C₆H₁₃ 93 CH₃ n-C₇H₁₅ 94 C₂H₅ CH₃ 95 C₂H₅ C₂H₅ 96 C₂H₅ n-C₃H₇ 97 C₂H₅ n-C₄H₉ 98 C₂H₅ n-C₅H₁₁ 99 C₂H₅ n-C₆H₁₃ 100 C₂H₅ n-C₇H₁₅ 101 n-C₃H₇ CH₃ 102 n-C₃H₇ C₂H₅ 103 n-C₃H₇ n-C₃H₇ 104 n-C₃H₇ n-C₄H₉ 105 n-C₃H₇ n-C₅H₁₁ 106 n-C₃H₇ n-C₆H₁₃ 107 n-C₃H₇ n-C₇H₁₅ 108 n-C₄H₉ CH₃ 109 n-C₄H₉ C₂H₅ 110 n-C₄H₉ n-C₃H₇ 111 n-C₄H₉ n-C₄H₉ 112 n-C₄H₉ n-C₅H₁₁ 113 n-C₄H₉ n-C₆H₁₃ 114 n-C₄H₉ n-C₇H₁₅ 115 n-C₅H₁₁ CH₃ 116 n-C₅H₁₁ C₂H₅ 117 n-C₅H₁₁ n-C₃H₇ 118 n-C₅H₁₁ n-C₄H₉ 119 n-C₅H₁₁ n-C₅H₁₁ 120 n-C₅H₁₁ n-C₆H₁₃ 121 n-C₅H₁₁ n-C₇H₁₅ 122 n-C₆H₁₃ CH₃ 123 n-C₆H₁₃ C₂H₅ 124 n-C₆H₁₃ n-C₃H₇ 125 n-C₆H₁₃ n-C₄H₉ 126 n-C₆H₁₃ n-C₅H₁₁ 127 n-C₆H₁₃ n-C₆H₁₃ 128 n-C₆H₁₃ n-C₇H₁₅ 129 n-C₇H₁₅ CH₃ 130 n-C₇H₁₅ C₂H₅ 131 n-C₇H₁₅ n-C₃H₇ 132 n-C₇H₁₅ n-C₄H₉ 133 n-C₇H₁₅ n-C₅H₁₁ 134 n-C₇H₁₅ n-C₆H₁₃ 135 n-C₇H₁₅ n-C₇H₁₅ 136 CH₃O CH₃ 137 CH₃O C₂H₅ 138 CH₃O n-C₃H₇ 139 CH₃O n-C₄H₉ 140 CH₃O n-C₅H₁₁ 141 CH₃O n-C₆H₁₃ 142 CH₃O n-C₇H₁₅ 143 C₂H₅O CH₃ 144 C₂H₅O C₂H₅ 145 C₂H₅O n-C₃H₇ 146 C₂H₅O n-C₄H₉ 147 C₂H₅O n-C₅H₁₁ 148 C₂H₅O n-C₆H₁₃ 149 C₂H₅O n-C₇H₁₅ 150 CH₂═CH CH₃ 151 CH₂═CH C₂H₅ 152 CH₂═CH n-C₃H₇ 153 CH₂═CH n-C₄H₉ 154 CH₂═CH n-C₅H₁₁ 155 CH₂═CH n-C₆H₁₃ 156 CH₂═CH n-C₇H₁₅ 157 CH₃—CH═CH CH₃ 158 CH₃—CH═CH C₂H₅ 159 CH₃—CH═CH n-C₃H₇ 160 CH₃—CH═CH n-C₄H₉ 161 CH₃—CH═CH n-C₅H₁₁ 162 CH₃—CH═CH n-C₆H₁₃ 163 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 164 to 239

The following are prepared analogously to Examples 2 and 4:

Phase sequence No. R¹ R² T/° C. 164 CH₃ CH₃ 165 CH₃ C₂H₅ 166 CH₃ n-C₃H₇ 167 CH₃ n-C₄H₉ 168 CH₃ n-C₅H₁₁ 169 CH₃ n-C₆H₁₃ 170 CH₃ n-C₇H₁₅ 171 C₂H₅ CH₃ 172 C₂H₅ C₂H₅ 173 C₂H₅ n-C₃H₇ 174 C₂H₅ n-C₄H₉ 175 C₂H₅ n-C₅H₁₁ 176 C₂H₅ n-C₆H₁₃ 177 C₂H₅ n-C₇H₁₅ 178 n-C₃H₇ CH₃ 179 n-C₃H₇ C₂H₅ 180 n-C₃H₇ n-C₃H₇ 181 n-C₃H₇ n-C₄H₉ 4 n-C₃H₇ n-C₅H₁₁ C 101 I 182 n-C₃H₇ n-C₆H₁₃ 183 n-C₃H₇ n-C₇H₁₅ 184 n-C₄H₉ CH₃ 185 n-C₄H₉ C₂H₅ 186 n-C₄H₉ n-C₃H₇ 187 n-C₄H₉ n-C₄H₉ 188 n-C₄H₉ n-C₅H₁₁ 189 n-C₄H₉ n-C₆H₁₃ 190 n-C₄H₉ n-C₇H₁₅ 191 n-C₅H₁₁ CH₃ 192 n-C₅H₁₁ C₂H₅ 193 n-C₅H₁₁ n-C₃H₇ 208 n-C₅H₁₁ n-C₄H₉ 209 n-C₅H₁₁ n-C₅H₁₁ 210 n-C₅H₁₁ n-C₆H₁₃ 211 n-C₅H₁₁ n-C₇H₁₅ 212 n-C₆H₁₃ CH₃ 213 n-C₆H₁₃ C₂H₅ 214 n-C₆H₁₃ n-C₃H₇ 215 n-C₆H₁₃ n-C₄H₉ 216 n-C₆H₁₃ n-C₅H₁₁ 217 n-C₆H₁₃ n-C₆H₁₃ 218 n-C₆H₁₃ n-C₇H₁₅ 219 n-C₇H₁₅ CH₃ 220 n-C₇H₁₅ C₂H₅ 221 n-C₇H₁₅ n-C₃H₇ 222 n-C₇H₁₅ n-C₄H₉ 223 n-C₇H₁₅ n-C₅H₁₁ 224 n-C₇H₁₅ n-C₆H₁₃ 225 n-C₇H₁₅ n-C₇H₁₅ 226 CH₃O CH₃ 227 CH₃O C₂H₅ 228 CH₃O n-C₃H₇ 229 CH₃O n-C₄H₉ 230 CH₃O n-C₅H₁₁ 231 CH₃O n-C₆H₁₃ 232 CH₃O n-C₇H₁₅ 233 C₂H₅O CH₃ 234 C₂H₅O C₂H₅ 235 C₂H₅O n-C₃H₇ 236 C₂H₅O n-C₄H₉ 237 C₂H₅O n-C₅H₁₁ 238 C₂H₅O n-C₆H₁₃ 239 C₂H₅O n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 240 to 302

The following are prepared analogously to Examples 2 and 4:

Phase sequence No. R¹ R² T/° C. 240 CH₃ CH₃ 241 CH₃ C₂H₅ 242 CH₃ n-C₃H₇ 243 CH₃ n-C₄H₉ 244 CH₃ n-C₅H₁₁ 245 CH₃ n-C₆H₁₃ 246 CH₃ n-C₇H₁₅ 247 C₂H₅ CH₃ 248 C₂H₅ C₂H₅ 249 C₂H₅ n-C₃H₇ 250 C₂H₅ n-C₄H₉ 251 C₂H₅ n-C₅H₁₁ 252 C₂H₅ n-C₆H₁₃ 253 C₂H₅ n-C₇H₁₅ 254 n-C₃H₇ CH₃ 255 n-C₃H₇ C₂H₅ 256 n-C₃H₇ n-C₃H₇ 257 n-C₃H₇ n-C₄H₉ 258 n-C₃H₇ n-C₅H₁₁ 259 n-C₃H₇ n-C₆H₁₃ 260 n-C₃H₇ n-C₇H₁₅ 261 n-C₄H₉ CH₃ 262 n-C₄H₉ C₂H₅ 263 n-C₄H₉ n-C₃H₇ 264 n-C₄H₉ n-C₄H₉ 265 n-C₄H₉ n-C₅H₁₁ 266 n-C₄H₉ n-C₆H₁₃ 267 n-C₄H₉ n-C₇H₁₅ 268 n-C₅H₁₁ CH₃ 269 n-C₅H₁₁ C₂H₅ 270 n-C₅H₁₁ n-C₃H₇ 271 n-C₅H₁₁ n-C₄H₉ 272 n-C₅H₁₁ n-C₅H₁₁ 273 n-C₅H₁₁ n-C₆H₁₃ 274 n-C₅H₁₁ n-C₇H₁₅ 275 n-C₆H₁₃ CH₃ 276 n-C₆H₁₃ C₂H₅ 277 n-C₆H₁₃ n-C₃H₇ 278 n-C₆H₁₃ n-C₄H₉ 279 n-C₆H₁₃ n-C₅H₁₁ 280 n-C₆H₁₃ n-C₆H₁₃ 281 n-C₆H₁₃ n-C₇H₁₅ 282 n-C₇H₁₅ CH₃ 283 n-C₇H₁₅ C₂H₅ 284 n-C₇H₁₅ n-C₃H₇ 285 n-C₇H₁₅ n-C₄H₉ 286 n-C₇H₁₅ n-C₅H₁₁ 287 n-C₇H₁₅ n-C₆H₁₃ 288 n-C₇H₁₅ n-C₇H₁₅ 289 CH₃O CH₃ 290 CH₃O C₂H₅ 291 CH₃O n-C₃H₇ 292 CH₃O n-C₄H₉ 293 CH₃O n-C₅H₁₁ 294 CH₃O n-C₆H₁₃ 295 CH₃O n-C₇H₁₅ 296 C₂H₅O CH₃ 297 C₂H₅O C₂H₅ 298 C₂H₅O n-C₃H₇ 299 C₂H₅O n-C₄H₉ 300 C₂H₅O n-C₅H₁₁ 300 C₂H₅O n-C₆H₁₃ 302 C₂H₅O n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 303 to 307

The following are prepared analogously to Examples 5 and 7:

No. R² Phase sequence T/° C. 303 CH₃ 304 C₂H₅ 5 n-C₃H₇ C 75 I 305 n-C₄H₉ 7 n-C₅H₁₁ C 61 I 306 n-C₆H₁₃ 307 n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 308 to 314

The following are prepared analogously to Examples 5 and 7:

No. R² Phase sequence T/° C. 308 CH₃ 309 C₂H₅ 310 n-C₃H₇ 311 n-C₄H₉ 312 n-C₅H₁₁ 313 n-C₆H₁₃ 314 n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 315 to 319

The following are prepared analogously to Examples 6 and 8:

No. R² Phase sequence T/° C. 315 CH₃ 316 C₂H₅ 6 n-C₃H₇ C 87 I 317 n-C₄H₉ 8 n-C₅H₁₁ C 76 I 318 n-C₆H₁₃ 319 n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 320 to 325

The following are prepared analogously to Examples 6 and 8:

No. R² Phase sequence T/° C. 320 CH₃ 241 C₂H₅ 321 n-C₃H₇ 322 n-C₄H₉ 323 n-C₅H₁₁ 324 n-C₆H₁₃ 325 n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 326 to 381

The following are prepared analogously to Examples 1, 3 and 9:

Phase sequence No. R¹ R² T/° C. 326 C₂H₅ CH₃ 327 C₂H₅ C₂H₅ 328 C₂H₅ n-C₃H₇ 329 C₂H₅ n-C₄H₉ 330 C₂H₅ n-C₅H₁₁ 331 C₂H₅ n-C₆H₁₃ 332 C₂H₅ n-C₇H₁₅ 333 n-C₃H₇ CH₃ 334 n-C₃H₇ C₂H₅ 335 n-C₃H₇ n-C₃H₇ 336 n-C₃H₇ n-C₄H₉ 337 n-C₃H₇ n-C₅H₁₁ 338 n-C₃H₇ n-C₆H₁₃ 339 n-C₃H₇ n-C₇H₁₅ 340 n-C₄H₉ CH₃ 341 n-C₄H₉ C₂H₅ 342 n-C₄H₉ n-C₃H₇ 343 n-C₄H₉ n-C₄H₉ 344 n-C₄H₉ n-C₅H₁₁ 345 n-C₄H₉ n-C₆H₁₃ 346 n-C₄H₉ n-C₇H₁₅ 347 n-C₅H₁₁ CH₃ 348 n-C₅H₁₁ C₂H₅ 349 n-C₅H₁₁ n-C₃H₇ 350 n-C₅H₁₁ n-C₄H₉ 351 n-C₅H₁₁ n-C₅H₁₁ 352 n-C₅H₁₁ n-C₆H₁₃ 353 n-C₅H₁₁ n-C₇H₁₅ 354 n-C₆H₁₃ CH₃ 355 n-C₆H₁₃ C₂H₅ 356 n-C₆H₁₃ n-C₃H₇ 357 n-C₆H₁₃ n-C₄H₉ 358 n-C₆H₁₃ n-C₅H₁₁ 359 n-C₆H₁₃ n-C₆H₁₃ 360 n-C₆H₁₃ n-C₇H₁₅ 361 n-C₇H₁₅ CH₃ 362 n-C₇H₁₅ C₂H₅ 363 n-C₇H₁₅ n-C₃H₇ 364 n-C₇H₁₅ n-C₄H₉ 365 n-C₇H₁₅ n-C₅H₁₁ 366 n-C₇H₁₅ n-C₆H₁₃ 367 n-C₇H₁₅ n-C₇H₁₅ 368 CH₂═CH CH₃ 369 CH₂═CH C₂H₅ 370 CH₂═CH n-C₃H₇ 371 CH₂═CH n-C₄H₉ 372 CH₂═CH n-C₅H₁₁ 373 CH₂═CH n-C₆H₁₃ 374 CH₂═CH n-C₇H₁₅ 375 CH₃—CH═CH CH₃ 376 CH₃—CH═CH C₂H₅ 377 CH₃—CH═CH n-C₃H₇ 378 CH₃—CH═CH n-C₄H₉ 379 CH₃—CH═CH n-C₅H₁₁ 380 CH₃—CH═CH n-C₆H₁₃ 381 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 382 to 437

The following are prepared analogously to Examples 1, 3 and 9:

Phase sequence No. R¹ R² T/° C. 382 C₂H₅ CH₃ 383 C₂H₅ C₂H₅ 394 C₂H₅ n-C₃H₇ 395 C₂H₅ n-C₄H₉ 396 C₂H₅ n-C₅H₁₁ 397 C₂H₅ n-C₆H₁₃ 398 C₂H₅ n-C₇H₁₅ 399 n-C₃H₇ CH₃ 390 n-C₃H₇ C₂H₅ 391 n-C₃H₇ n-C₃H₇ 392 n-C₃H₇ n-C₄H₉ 393 n-C₃H₇ n-C₅H₁₁ 394 n-C₃H₇ n-C₆H₁₃ 395 n-C₃H₇ n-C₇H₁₅ 396 n-C₄H₉ CH₃ 397 n-C₄H₉ C₂H₅ 398 n-C₄H₉ n-C₃H₇ 399 n-C₄H₉ n-C₄H₉ 400 n-C₄H₉ n-C₅H₁₁ 401 n-C₄H₉ n-C₆H₁₃ 402 n-C₄H₉ n-C₇H₁₅ 403 n-C₅H₁₁ CH₃ 404 n-C₅H₁₁ C₂H₅ 405 n-C₅H₁₁ n-C₃H₇ 406 n-C₅H₁₁ n-C₄H₉ 407 n-C₅H₁₁ n-C₅H₁₁ 408 n-C₅H₁₁ n-C₆H₁₃ 409 n-C₅H₁₁ n-C₇H₁₅ 410 n-C₆H₁₃ CH₃ 411 n-C₆H₁₃ C₂H₅ 412 n-C₆H₁₃ n-C₃H₇ 413 n-C₆H₁₃ n-C₄H₉ 414 n-C₆H₁₃ n-C₅H₁₁ 415 n-C₆H₁₃ n-C₆H₁₃ 416 n-C₆H₁₃ n-C₇H₁₅ 417 n-C₇H₁₅ CH₃ 418 n-C₇H₁₅ C₂H₅ 419 n-C₇H₁₅ n-C₃H₇ 420 n-C₇H₁₅ n-C₄H₉ 421 n-C₇H₁₅ n-C₅H₁₁ 422 n-C₇H₁₅ n-C₆H₁₃ 423 n-C₇H₁₅ n-C₇H₁₅ 424 CH₂═CH CH₃ 425 CH₂═CH C₂H₅ 426 CH₂═CH n-C₃H₇ 427 CH₂═CH n-C₄H₉ 428 CH₂═CH n-C₅H₁₁ 429 CH₂═CH n-C₆H₁₃ 430 CH₂═CH n-C₇H₁₅ 431 CH₃—CH═CH CH₃ 432 CH₃—CH═CH C₂H₅ 453 CH₃—CH═CH n-C₃H₇ 434 CH₃—CH═CH n-C₄H₉ 435 CH₃—CH═CH n-C₅H₁₁ 436 CH₃—CH═CH n-C₆H₁₃ 437 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 438 to 480

The following are prepared analogously to Examples 2 and 4:

Phase sequence No. R¹ R² T/° C. 438 CH₃ n-C₇H₁₅ 439 C₂H₅ CH₃ 440 C₂H₅ C₂H₅ 441 C₂H₅ n-C₃H₇ 442 C₂H₅ n-C₄H₉ 443 C₂H₅ n-C₅H₁₁ 444 C₂H₅ n-C₆H₁₃ 445 C₂H₅ n-C₇H₁₅ 446 n-C₃H₇ CH₃ 447 n-C₃H₇ C₂H₅ 448 n-C₃H₇ n-C₃H₇ 449 n-C₃H₇ n-C₄H₉ 450 n-C₃H₇ n-C₅H₁₁ 451 n-C₃H₇ n-C₆H₁₃ 452 n-C₃H₇ n-C₇H₁₅ 453 n-C₄H₉ CH₃ 454 n-C₄H₉ C₂H₅ 455 n-C₄H₉ n-C₃H₇ 456 n-C₄H₉ n-C₄H₉ 457 n-C₄H₉ n-C₅H₁₁ 458 n-C₄H₉ n-C₆H₁₃ 459 n-C₄H₉ n-C₇H₁₅ 460 n-C₅H₁₁ CH₃ 461 n-C₅H₁₁ C₂H₅ 462 n-C₅H₁₁ n-C₃H₇ 463 n-C₅H₁₁ n-C₄H₉ 464 n-C₅H₁₁ n-C₅H₁₁ 465 n-C₅H₁₁ n-C₆H₁₃ 466 n-C₅H₁₁ n-C₇H₁₅ 467 n-C₆H₁₃ CH₃ 468 n-C₆H₁₃ C₂H₅ 469 n-C₆H₁₃ n-C₃H₇ 470 n-C₆H₁₃ n-C₄H₉ 471 n-C₆H₁₃ n-C₅H₁₁ 472 n-C₆H₁₃ n-C₆H₁₃ 473 n-C₆H₁₃ n-C₇H₁₅ 474 n-C₇H₁₅ CH₃ 475 n-C₇H₁₅ C₂H₅ 476 n-C₇H₁₅ n-C₃H₇ 477 n-C₇H₁₅ n-C₄H₉ 478 n-C₇H₁₅ n-C₅H₁₁ 479 n-C₇H₁₅ n-C₆H₁₃ 480 n-C₇H₁₅ n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 481 to 523

The following are prepared analogously to Examples 2 and 4:

Phase sequence No. R¹ R² T/° C. 481 CH₃ n-C₇H₁₅ 482 C₂H₅ CH₃ 483 C₂H₅ C₂H₅ 484 C₂H₅ n-C₃H₇ 485 C₂H₅ n-C₄H₉ 486 C₂H₅ n-C₅H₁₁ 487 C₂H₅ n-C₆H₁₃ 488 C₂H₅ n-C₇H₁₅ 489 n-C₃H₇ CH₃ 490 n-C₃H₇ C₂H₅ 491 n-C₃H₇ n-C₃H₇ 492 n-C₃H₇ n-C₄H₉ 493 n-C₃H₇ n-C₅H₁₁ 494 n-C₃H₇ n-C₆H₁₃ 495 n-C₃H₇ n-C₇H₁₅ 496 n-C₄H₉ CH₃ 497 n-C₄H₉ C₂H₅ 498 n-C₄H₉ n-C₃H₇ 499 n-C₄H₉ n-C₄H₉ 500 n-C₄H₉ n-C₅H₁₁ 501 n-C₄H₉ n-C₆H₁₃ 502 n-C₄H₉ n-C₇H₁₅ 503 n-C₅H₁₁ CH₃ 504 n-C₅H₁₁ C₂H₅ 505 n-C₅H₁₁ n-C₃H₇ 586 n-C₅H₁₁ n-C₄H₉ 507 n-C₅H₁₁ n-C₅H₁₁ 508 n-C₅H₁₁ n-C₆H₁₃ 509 n-C₅H₁₁ n-C₇H₁₅ 510 n-C₆H₁₃ CH₃ 511 n-C₆H₁₃ C₂H₅ 512 n-C₆H₁₃ n-C₃H₇ 513 n-C₆H₁₃ n-C₄H₉ 514 n-C₆H₁₃ n-C₅H₁₁ 515 n-C₆H₁₃ n-C₆H₁₃ 516 n-C₆H₁₃ n-C₇H₁₅ 517 n-C₇H₁₅ CH₃ 518 n-C₇H₁₅ C₂H₅ 519 n-C₇H₁₅ n-C₃H₇ 520 n-C₇H₁₅ n-C₄H₉ 521 n-C₇H₁₅ n-C₅H₁₁ 522 n-C₇H₁₅ n-C₆H₁₃ 523 n-C₇H₁₅ n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 524 to 599

The following are prepared analogously to Example 9:

Phase sequence No. R¹ R² T/° C. 524 CH₃ CH₃ 525 CH₃ C₂H₅ 526 CH₃ n-C₃H₇ 527 CH₃ n-C₄H₉ 528 CH₃ n-C₅H₁₁ 529 CH₃ n-C₆H₁₃ 530 CH₃ n-C₇H₁₅ 531 C₂H₅ CH₃ 532 C₂H₅ C₂H₅ 533 C₂H₅ n-C₃H₇ 534 C₂H₅ n-C₄H₉ 535 C₂H₅ n-C₅H₁₁ 536 C₂H₅ n-C₆H₁₃ 537 C₂H₅ n-C₇H₁₅ 538 n-C₃H₇ CH₃ 539 n-C₃H₇ C₂H₅ 540 n-C₃H₇ n-C₃H₇ 541 n-C₃H₇ n-C₄H₉ 9 n-C₃H₇ n-C₅H₁₁ T_(g) −31 C 70 N 79 I 542 n-C₃H₇ n-C₆H₁₃ 543 n-C₃H₇ n-C₇H₁₅ 544 n-C₄H₉ CH₃ 545 n-C₄H₉ C₂H₅ 546 n-C₄H₉ n-C₃H₇ 547 n-C₄H₉ n-C₄H₉ 548 n-C₄H₉ n-C₅H₁₁ 549 n-C₄H₉ n-C₆H₁₃ 550 n-C₄H₉ n-C₇H₁₅ 551 n-C₅H₁₁ CH₃ 552 n-C₅H₁₁ C₂H₅ 553 n-C₅H₁₁ n-C₃H₇ 554 n-C₅H₁₁ n-C₄H₉ 555 n-C₅H₁₁ n-C₅H₁₁ 556 n-C₅H₁₁ n-C₆H₁₃ 557 n-C₅H₁₁ n-C₇H₁₅ 558 n-C₆H₁₃ CH₃ 559 n-C₆H₁₃ C₂H₅ 560 n-C₆H₁₃ n-C₃H₇ 561 n-C₆H₁₃ n-C₄H₉ 562 n-C₆H₁₃ n-C₅H₁₁ 563 n-C₆H₁₃ n-C₆H₁₃ 564 n-C₆H₁₃ n-C₇H₁₅ 565 n-C₇H₁₅ CH₃ 566 n-C₇H₁₅ C₂H₅ 567 n-C₇H₁₅ n-C₃H₇ 568 n-C₇H₁₅ n-C₄H₉ 569 n-C₇H₁₅ n-C₅H₁₁ 570 n-C₇H₁₅ n-C₆H₁₃ 571 n-C₇H₁₅ n-C₇H₁₅ 572 CH₃O CH₃ 573 CH₃O C₂H₅ 574 CH₃O n-C₃H₇ 575 CH₃O n-C₄H₉ 576 CH₃O n-C₅H₁₁ 577 CH₃O n-C₆H₁₃ 578 CH₃O n-C₇H₁₅ 579 C₂H₅O CH₃ 580 C₂H₅O C₂H₅ 581 C₂H₅O n-C₃H₇ 582 C₂H₅O n-C₄H₉ 583 C₂H₅O n-C₅H₁₁ 584 C₂H₅O n-C₆H₁₃ 599 C₂H₅O n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 600 to 676

The following are prepared analogously to Example 9:

Phase sequence No. R¹ R² T/° C. 600 CH₃ CH₃ 601 CH₃ C₂H₅ 602 CH₃ n-C₃H₇ 603 CH₃ n-C₄H₉ 604 CH₃ n-C₅H₁₁ 605 CH₃ n-C₆H₁₃ 606 CH₃ n-C₇H₁₅ 607 C₂H₅ CH₃ 608 C₂H₅ C₂H₅ 609 C₂H₅ n-C₃H₇ 610 C₂H₅ n-C₄H₉ 611 C₂H₅ n-C₅H₁₁ 612 C₂H₅ n-C₆H₁₃ 613 C₂H₅ n-C₇H₁₅ 614 n-C₃H₇ CH₃ 615 n-C₃H₇ C₂H₅ 616 n-C₃H₇ n-C₃H₇ 617 n-C₃H₇ n-C₄H₉ 618 n-C₃H₇ n-C₅H₁₁ 619 n-C₃H₇ n-C₆H₁₃ 620 n-C₃H₇ n-C₇H₁₅ 621 n-C₄H₉ CH₃ 622 n-C₄H₉ C₂H₅ 623 n-C₄H₉ n-C₃H₇ 624 n-C₄H₉ n-C₄H₉ 625 n-C₄H₉ n-C₅H₁₁ 626 n-C₄H₉ n-C₆H₁₃ 627 n-C₄H₉ n-C₇H₁₅ 628 n-C₅H₁₁ CH₃ 629 n-C₅H₁₁ C₂H₅ 630 n-C₅H₁₁ n-C₃H₇ 631 n-C₅H₁₁ n-C₄H₉ 632 n-C₅H₁₁ n-C₅H₁₁ 633 n-C₅H₁₁ n-C₆H₁₃ 634 n-C₅H₁₁ n-C₇H₁₅ 635 n-C₆H₁₃ CH₃ 636 n-C₆H₁₃ C₂H₅ 637 n-C₆H₁₃ n-C₃H₇ 638 n-C₆H₁₃ n-C₄H₉ 639 n-C₆H₁₃ n-C₅H₁₁ 640 n-C₆H₁₃ n-C₆H₁₃ 641 n-C₆H₁₃ n-C₇H₁₅ 642 n-C₇H₁₅ CH₃ 643 n-C₇H₁₅ C₂H₅ 644 n-C₇H₁₅ n-C₃H₇ 645 n-C₇H₁₅ n-C₄H₉ 646 n-C₇H₁₅ n-C₅H₁₁ 677 n-C₇H₁₅ n-C₆H₁₃ 648 n-C₇H₁₅ n-C₇H₁₅ 649 CH₃O CH₃ 650 CH₃O C₂H₅ 651 CH₃O n-C₃H₇ 652 CH₃O n-C₄H₉ 653 CH₃O n-C₅H₁₁ 654 CH₃O n-C₆H₁₃ 669 CH₃O n-C₇H₁₅ 670 C₂H₅O CH₃ 671 C₂H₅O C₂H₅ 672 C₂H₅O n-C₃H₇ 673 C₂H₅O n-C₄H₉ 674 C₂H₅O n-C₅H₁₁ 675 C₂H₅O n-C₆H₁₃ 676 C₂H₅O n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 677 to 753

The following are prepared from 31 analogously to Examples 1, 3 and 9:

No. R¹ R² Phase sequence T/° C. 677 CH₃ CH₃ 678 CH₃ C₂H₅ 679 CH₃ n-C₃H₇ 680 CH₃ n-C₄H₉ 681 CH₃ n-C₅H₁₁ 682 CH₃ n-C₆H₁₃ 683 CH₃ n-C₇H₁₅ 684 C₂H₅ CH₃ 685 C₂H₅ C₂H₅ 686 C₂H₅ n-C₃H₇ 687 C₂H₅ n-C₄H₉ 688 C₂H₅ n-C₅H₁₁ 689 C₂H₅ n-C₆H₁₃ 690 C₂H₅ n-C₇H₁₅ 691 n-C₃H₇ CH₃ 692 n-C₃H₇ C₂H₅ 693 n-C₃H₇ n-C₃H₇ 694 n-C₃H₇ n-C₄H₉ 695 n-C₃H₇ n-C₅H₁₁ 696 n-C₃H₇ n-C₆H₁₃ 697 n-C₃H₇ n-C₇H₁₅ 698 n-C₄H₉ CH₃ 699 n-C₄H₉ C₂H₅ 700 n-C₄H₉ n-C₃H₇ 701 n-C₄H₉ n-C₄H₉ 702 n-C₄H₉ n-C₅H₁₁ 703 n-C₄H₉ n-C₆H₁₃ 704 n-C₄H₉ n-C₇H₁₅ 705 n-C₅H₁₁ CH₃ 706 n-C₅H₁₁ C₂H₅ 707 n-C₅H₁₁ n-C₃H₇ 708 n-C₅H₁₁ n-C₄H₉ 709 n-C₅H₁₁ n-C₅H₁₁ 710 n-C₅H₁₁ n-C₆H₁₃ 711 n-C₅H₁₁ n-C₇H₁₅ 712 n-C₆H₁₃ CH₃ 713 n-C₆H₁₃ C₂H₅ 714 n-C₆H₁₃ n-C₃H₇ 715 n-C₆H₁₃ n-C₄H₉ 716 n-C₆H₁₃ n-C₅H₁₁ 717 n-C₆H₁₃ n-C₆H₁₃ 718 n-C₆H₁₃ n-C₇H₁₅ 719 n-C₇H₁₅ CH₃ 720 n-C₇H₁₅ C₂H₅ 721 n-C₇H₁₅ n-C₃H₇ 722 n-C₇H₁₅ n-C₄H₉ 723 n-C₇H₁₅ n-C₅H₁₁ 724 n-C₇H₁₅ n-C₆H₁₃ 725 n-C₇H₁₅ n-C₇H₁₅ 726 CH₃O CH₃ 727 CH₃O C₂H₅ 728 CH₃O n-C₃H₇ 729 CH₃O n-C₄H₉ 730 CH₃O n-C₅H₁₁ 731 CH₃O n-C₆H₁₃ 732 CH₃O n-C₇H₁₅ 733 C₂H₅O CH₃ 734 C₂H₅O C₂H₅ 735 C₂H₅O n-C₃H₇ 736 C₂H₅O n-C₄H₉ 737 C₂H₅O n-C₅H₁₁ 738 C₂H₅O n-C₆H₁₃ 739 C₂H₅O n-C₇H₁₅ 740 CH₂═CH CH₃ 741 CH₂═CH C₂H₅ 742 CH₂═CH n-C₃H₇ 743 CH₂═CH n-C₄H₉ 744 CH₂═CH n-C₅H₁₁ 745 CH₂═CH n-C₆H₁₃ 746 CH₂═CH n-C₇H₁₅ 747 CH₃—CH═CH CH₃ 748 CH₃—CH═CH C₂H₅ 749 CH₃—CH═CH n-C₃H₇ 750 CH₃—CH═CH n-C₄H₉ 751 CH₃—CH═CH n-C₅H₁₁ 752 CH₃—CH═CH n-C₆H₁₃ 753 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 754 to 821

The following are prepared from 36 analogously to Examples 1, 3 and 9:

No. R¹ R² Phase sequence T/° C. 754 CH₃ CH₃ 755 CH₃ C₂H₅ 756 CH₃ n-C₃H₇ 757 CH₃ n-C₄H₉ 758 CH₃ n-C₅H₁₁ 759 CH₃ n-C₆H₁₃ 760 CH₃ n-C₇H₁₅ 761 C₂H₅ CH₃ 762 C₂H₅ C₂H₅ 763 C₂H₅ n-C₃H₇ 764 C₂H₅ n-C₄H₉ 765 C₂H₅ n-C₅H₁₁ 766 C₂H₅ n-C₆H₁₃ 767 C₂H₅ n-C₇H₁₅ 768 n-C₃H₇ CH₃ 769 n-C₃H₇ C₂H₅ 770 n-C₃H₇ n-C₃H₇ 771 n-C₃H₇ n-C₄H₉ 772 n-C₃H₇ n-C₅H₁₁ 773 n-C₃H₇ n-C₆H₁₃ 774 n-C₃H₇ n-C₇H₁₅ 775 n-C₄H₉ CH₃ 776 n-C₄H₉ C₂H₅ 777 n-C₄H₉ n-C₃H₇ 778 n-C₄H₉ n-C₄H₉ 779 n-C₄H₉ n-C₅H₁₁ 780 n-C₄H₉ n-C₆H₁₃ 781 n-C₄H₉ n-C₇H₁₅ 782 n-C₅H₁₁ CH₃ 783 n-C₅H₁₁ C₂H₅ 784 n-C₅H₁₁ n-C₃H₇ 785 n-C₅H₁₁ n-C₄H₉ 786 n-C₅H₁₁ n-C₅H₁₁ 787 n-C₅H₁₁ n-C₆H₁₃ 788 n-C₅H₁₁ n-C₇H₁₅ 789 n-C₆H₁₃ CH₃ 790 n-C₆H₁₃ C₂H₅ 791 n-C₆H₁₃ n-C₃H₇ 792 n-C₆H₁₃ n-C₄H₉ 793 n-C₆H₁₃ n-C₅H₁₁ 794 n-C₆H₁₃ n-C₆H₁₃ 795 n-C₆H₁₃ n-C₇H₁₅ 796 n-C₇H₁₅ CH₃ 797 n-C₇H₁₅ C₂H₅ 798 n-C₇H₁₅ n-C₃H₇ 799 n-C₇H₁₅ n-C₄H₉ 800 n-C₇H₁₅ n-C₅H₁₁ 801 n-C₇H₁₅ n-C₆H₁₃ 802 n-C₇H₁₅ n-C₇H₁₅ 803 CH₃O CH₃ 804 CH₃O C₂H₅ 806 CH₃O n-C₃H₇ 807 CH₃O n-C₄H₉ 808 CH₃O n-C₅H₁₁ 809 CH₃O n-C₆H₁₃ 810 CH₃O n-C₇H₁₅ 811 C₂H₅O CH₃ 812 C₂H₅O C₂H₅ 813 C₂H₅O n-C₃H₇ 814 C₂H₅O n-C₄H₉ 815 C₂H₅O n-C₅H₁₁ 816 C₂H₅O n-C₆H₁₃ 817 C₂H₅O n-C₇H₁₅ 818 CH₂═CH CH₃ 819 CH₂═CH C₂H₅ 820 CH₂═CH n-C₃H₇ 821 CH₂═CH n-C₄H₉ 822 CH₂═CH n-C₅H₁₁ 823 CH₂═CH n-C₆H₁₃ 824 CH₂═CH n-C₇H₁₅ 825 CH₃—CH═CH CH₃ 826 CH₃—CH═CH C₂H₅ 827 CH₃—CH═CH n-C₃H₇ 828 CH₃—CH═CH n-C₄H₉ 829 CH₃—CH═CH n-C₅H₁₁ 820 CH₃—CH═CH n-C₆H₁₃ 821 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 822 to 877

The following are prepared from 31 analogously to Examples 1, 3 and 9:

No. R¹ R² Phase sequence T/° C. 822 C₂H₅ CH₃ 823 C₂H₅ C₂H₅ 824 C₂H₅ n-C₃H₇ 825 C₂H₅ n-C₄H₉ 826 C₂H₅ n-C₅H₁₁ 827 C₂H₅ n-C₆H₁₃ 828 C₂H₅ n-C₇H₁₅ 829 n-C₃H₇ CH₃ 830 n-C₃H₇ C₂H₅ 831 n-C₃H₇ n-C₃H₇ 832 n-C₃H₇ n-C₄H₉ 833 n-C₃H₇ n-C₅H₁₁ 834 n-C₃H₇ n-C₆H₁₃ 835 n-C₃H₇ n-C₇H₁₅ 836 n-C₄H₉ CH₃ 837 n-C₄H₉ C₂H₅ 838 n-C₄H₉ n-C₃H₇ 839 n-C₄H₉ n-C₄H₉ 840 n-C₄H₉ n-C₅H₁₁ 841 n-C₄H₉ n-C₆H₁₃ 842 n-C₄H₉ n-C₇H₁₅ 843 n-C₅H₁₁ CH₃ 844 n-C₅H₁₁ C₂H₅ 845 n-C₅H₁₁ n-C₃H₇ 846 n-C₅H₁₁ n-C₄H₉ 847 n-C₅H₁₁ n-C₅H₁₁ 848 n-C₅H₁₁ n-C₆H₁₃ 849 n-C₅H₁₁ n-C₇H₁₅ 850 n-C₆H₁₃ CH₃ 851 n-C₆H₁₃ C₂H₅ 852 n-C₆H₁₃ n-C₃H₇ 853 n-C₆H₁₃ n-C₄H₉ 854 n-C₆H₁₃ n-C₅H₁₁ 855 n-C₆H₁₃ n-C₆H₁₃ 856 n-C₆H₁₃ n-C₇H₁₅ 857 n-C₇H₁₅ CH₃ 858 n-C₇H₁₅ C₂H₅ 859 n-C₇H₁₅ n-C₃H₇ 860 n-C₇H₁₅ n-C₄H₉ 861 n-C₇H₁₅ n-C₅H₁₁ 862 n-C₇H₁₅ n-C₆H₁₃ 863 n-C₇H₁₅ n-C₇H₁₅ 864 CH₂═CH CH₃ 865 CH₂═CH C₂H₅ 866 CH₂═CH n-C₃H₇ 867 CH₂═CH n-C₄H₉ 868 CH₂═CH n-C₅H₁₁ 869 CH₂═CH n-C₆H₁₃ 870 CH₂═CH n-C₇H₁₅ 871 CH₃—CH═CH CH₃ 872 CH₃—CH═CH C₂H₅ 873 CH₃—CH═CH n-C₃H₇ 874 CH₃—CH═CH n-C₄H₉ 875 CH₃—CH═CH n-C₅H₁₁ 876 CH₃—CH═CH n-C₆H₁₃ 877 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 878 to 940

The following are prepared from 36 analogously to Examples 1, 3 and 9:

No. R¹ R² Phase sequence T/° C. 878 CH₃ CH₃ 879 CH₃ C₂H₅ 880 CH₃ n-C₃H₇ 881 CH₃ n-C₄H₉ 882 CH₃ n-C₅H₁₁ 883 CH₃ n-C₆H₁₃ 884 CH₃ n-C₇H₁₅ 885 C₂H₅ CH₃ 886 C₂H₅ C₂H₅ 887 C₂H₅ n-C₃H₇ 888 C₂H₅ n-C₄H₉ 889 C₂H₅ n-C₅H₁₁ 890 C₂H₅ n-C₆H₁₃ 891 C₂H₅ n-C₇H₁₅ 892 n-C₃H₇ CH₃ 893 n-C₃H₇ C₂H₅ 894 n-C₃H₇ n-C₃H₇ 895 n-C₃H₇ n-C₄H₉ 896 n-C₃H₇ n-C₅H₁₁ 897 n-C₃H₇ n-C₆H₁₃ 898 n-C₃H₇ n-C₇H₁₅ 899 n-C₄H₉ CH₃ 900 n-C₄H₉ C₂H₅ 901 n-C₄H₉ n-C₃H₇ 902 n-C₄H₉ n-C₄H₉ 903 n-C₄H₉ n-C₅H₁₁ 904 n-C₄H₉ n-C₆H₁₃ 905 n-C₄H₉ n-C₇H₁₅ 906 n-C₅H₁₁ CH₃ 907 n-C₅H₁₁ C₂H₅ 908 n-C₅H₁₁ n-C₃H₇ 909 n-C₅H₁₁ n-C₄H₉ 910 n-C₅H₁₁ n-C₅H₁₁ 911 n-C₅H₁₁ n-C₆H₁₃ 912 n-C₅H₁₁ n-C₇H₁₅ 913 n-C₆H₁₃ CH₃ 914 n-C₆H₁₃ C₂H₅ 915 n-C₆H₁₃ n-C₃H₇ 916 n-C₆H₁₃ n-C₄H₉ 917 n-C₆H₁₃ n-C₅H₁₁ 918 n-C₆H₁₃ n-C₆H₁₃ 919 n-C₆H₁₃ n-C₇H₁₅ 920 n-C₇H₁₅ CH₃ 921 n-C₇H₁₅ C₂H₅ 922 n-C₇H₁₅ n-C₃H₇ 923 n-C₇H₁₅ n-C₄H₉ 924 n-C₇H₁₅ n-C₅H₁₁ 925 n-C₇H₁₅ n-C₆H₁₃ 926 n-C₇H₁₅ n-C₇H₁₅ 927 CH₂═CH CH₃ 928 CH₂═CH C₂H₅ 929 CH₂═CH n-C₃H₇ 930 CH₂═CH n-C₄H₉ 931 CH₂═CH n-C₅H₁₁ 932 CH₂═CH n-C₆H₁₃ 933 CH₂═CH n-C₇H₁₅ 934 CH₃—CH═CH CH₃ 935 CH₃—CH═CH C₂H₅ 936 CH₃—CH═CH n-C₃H₇ 937 CH₃—CH═CH n-C₄H₉ 938 CH₃—CH═CH n-C₅H₁₁ 939 CH₃—CH═CH n-C₆H₁₃ 940 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 941 to 996

The following are prepared from 31 analogously to Examples 1, 3 and 9:

No. R¹ R² Phase sequence T/° C. 941 C₂H₅ CH₃ 942 C₂H₅ C₂H₅ 943 C₂H₅ n-C₃H₇ 944 C₂H₅ n-C₄H₉ 945 C₂H₅ n-C₅H₁₁ 946 C₂H₅ n-C₆H₁₃ 947 C₂H₅ n-C₇H₁₅ 948 n-C₃H₇ CH₃ 949 n-C₃H₇ C₂H₅ 950 n-C₃H₇ n-C₃H₇ 951 n-C₃H₇ n-C₄H₉ 952 n-C₃H₇ n-C₅H₁₁ 953 n-C₃H₇ n-C₆H₁₃ 954 n-C₃H₇ n-C₇H₁₅ 955 n-C₄H₉ CH₃ 956 n-C₄H₉ C₂H₅ 957 n-C₄H₉ n-C₃H₇ 958 n-C₄H₉ n-C₄H₉ 959 n-C₄H₉ n-C₅H₁₁ 960 n-C₄H₉ n-C₆H₁₃ 961 n-C₄H₉ n-C₇H₁₅ 962 n-C₅H₁₁ CH₃ 963 n-C₅H₁₁ C₂H₅ 964 n-C₅H₁₁ n-C₃H₇ 965 n-C₅H₁₁ n-C₄H₉ 966 n-C₅H₁₁ n-C₅H₁₁ 967 n-C₅H₁₁ n-C₆H₁₃ 968 n-C₅H₁₁ n-C₇H₁₅ 969 n-C₆H₁₃ CH₃ 970 n-C₆H₁₃ C₂H₅ 971 n-C₆H₁₃ n-C₃H₇ 972 n-C₆H₁₃ n-C₄H₉ 973 n-C₆H₁₃ n-C₅H₁₁ 974 n-C₆H₁₃ n-C₆H₁₃ 975 n-C₆H₁₃ n-C₇H₁₅ 976 n-C₇H₁₅ CH₃ 977 n-C₇H₁₅ C₂H₅ 978 n-C₇H₁₅ n-C₃H₇ 979 n-C₇H₁₅ n-C₄H₉ 980 n-C₇H₁₅ n-C₅H₁₁ 981 n-C₇H₁₅ n-C₆H₁₃ 982 n-C₇H₁₅ n-C₇H₁₅ 983 CH₂═CH CH₃ 984 CH₂═CH C₂H₅ 985 CH₂═CH n-C₃H₇ 986 CH₂═CH n-C₄H₉ 987 CH₂═CH n-C₅H₁₁ 988 CH₂═CH n-C₆H₁₃ 989 CH₂═CH n-C₇H₁₅ 990 CH₃—CH═CH CH₃ 991 CH₃—CH═CH C₂H₅ 992 CH₃—CH═CH n-C₃H₇ 993 CH₃—CH═CH n-C₄H₉ 994 CH₃—CH═CH n-C₅H₁₁ 995 CH₃—CH═CH n-C₆H₁₃ 996 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 997 to 1059

The following are prepared from 36 analogously to Examples 1, 3 and 9:

No. R¹ R² Phase sequence T/° C. 997 CH₃ CH₃ 998 CH₃ C₂H₅ 999 CH₃ n-C₃H₇ 1000 CH₃ n-C₄H₉ 1001 CH₃ n-C₅H₁₁ 1002 CH₃ n-C₆H₁₃ 1003 CH₃ n-C₇H₁₅ 1004 C₂H₅ CH₃ 1005 C₂H₅ C₂H₅ 1006 C₂H₅ n-C₃H₇ 1007 C₂H₅ n-C₉H₉ 1008 C₂H₅ n-C₅H₁₁ 1009 C₂H₅ n-C₆H₁₃ 1010 C₂H₅ n-C₇H₁₅ 1011 n-C₃H₇ CH₃ 1012 n-C₃H₇ C₂H₅ 1013 n-C₃H₇ n-C₃H₇ 1014 n-C₃H₇ n-C₄H₉ 1015 n-C₃H₇ n-C₅H₁₁ 1016 n-C₃H₇ n-C₆H₁₃ 1017 n-C₃H₇ n-C₇H₁₅ 1018 n-C₄H₉ CH₃ 1019 n-C₄H₉ C₂H₅ 1020 n-C₄H₉ n-C₃H₇ 1021 n-C₄H₉ n-C₄H₉ 1022 n-C₄H₉ n-C₅H₁₁ 1023 n-C₄H₉ n-C₆H₁₃ 1024 n-C₄H₉ n-C₇H₁₅ 1025 n-C₅H₁₁ CH₃ 1026 n-C₅H₁₁ C₂H₅ 1027 n-C₅H₁₁ n-C₃H₇ 1028 n-C₅H₁₁ n-C₄H₉ 1029 n-C₅H₁₁ n-C₅H₁₁ 1030 n-C₅H₁₁ n-C₆H₁₃ 1031 n-C₅H₁₁ n-C₇H₁₅ 1032 n-C₆H₁₃ CH₃ 1033 n-C₆H₁₃ C₂H₅ 1034 n-C₆H₁₃ n-C₃H₇ 1035 n-C₆H₁₃ n-C₄H₉ 1036 n-C₆H₁₃ n-C₅H₁₁ 1037 n-C₆H₁₃ n-C₆H₁₃ 1038 n-C₆H₁₃ n-C₇H₁₅ 1039 n-C₇H₁₅ CH₃ 1040 n-C₇H₁₅ C₂H₅ 1041 n-C₇H₁₅ n-C₃H₇ 1042 n-C₇H₁₅ n-C₄H₉ 1043 n-C₇H₁₅ n-C₅H₁₁ 1044 n-C₇H₁₅ n-C₆H₁₃ 1045 n-C₇H₁₅ n-C₇H₁₅ 1046 CH₂═CH CH₃ 1047 CH₂═CH C₂H₅ 1048 CH₂═CH n-C₃H₇ 1049 CH₂═CH n-C₄H₉ 1050 CH₂═CH n-C₅H₁₁ 1051 CH₂═CH n-C₆H₁₃ 1052 CH₂═CH n-C₇H₁₅ 1053 CH₃—CH═CH CH₃ 1054 CH₃—CH═CH C₂H₅ 1055 CH₃—CH═CH n-C₃H₇ 1056 CH₃—CH═CH n-C₄H₉ 1057 CH₃—CH═CH n-C₅H₁₁ 1058 CH₃—CH═CH n-C₆H₁₃ 1059 CH₃—CH═CH n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 1060 to 1122

The following are prepared from 31 analogously to Example 9:

No. R¹ R² Phase sequence T/° C. 1060 CH₃ CH₃ 1061 CH₃ C₂H₅ 1062 CH₃ n-C₃H₇ 1063 CH₃ n-C₄H₉ 1064 CH₃ n-C₅H₁₁ 1065 CH₃ n-C₆H₁₃ 1066 CH₃ n-C₇H₁₅ 1067 C₂H₅ CH₃ 1068 C₂H₅ C₂H₅ 1069 C₂H₅ n-C₃H₇ 1070 C₂H₅ n-C₄H₉ 1071 C₂H₅ n-C₅H₁₁ 1072 C₂H₅ n-C₆H₁₃ 1073 C₂H₅ n-C₇H₁₅ 1074 n-C₃H₇ CH₃ 1075 n-C₃H₇ C₂H₅ 1076 n-C₃H₇ n-C₃H₇ 1077 n-C₃H₇ n-C₄H₉ 1078 n-C₃H₇ n-C₅H₁₁ 1079 n-C₃H₇ n-C₆H₁₃ 1080 n-C₃H₇ n-C₇H₁₅ 1081 n-C₄H₉ CH₃ 1082 n-C₄H₉ C₂H₅ 1083 n-C₄H₉ n-C₃H₇ 1084 n-C₄H₉ n-C₄H₉ 1085 n-C₄H₉ n-C₅H₁₁ 1086 n-C₄H₉ n-C₆H₁₃ 1087 n-C₄H₉ n-C₇H₁₅ 1088 n-C₅H₁₁ CH₃ 1089 n-C₅H₁₁ C₂H₅ 1090 n-C₅H₁₁ n-C₃H₇ 1091 n-C₅H₁₁ n-C₄H₉ 1092 n-C₅H₁₁ n-C₅H₁₁ 1093 n-C₅H₁₁ n-C₆H₁₃ 1094 n-C₅H₁₁ n-C₇H₁₅ 1095 n-C₆H₁₃ CH₃ 1096 n-C₆H₁₃ C₂H₅ 1097 n-C₆H₁₃ n-C₃H₇ 1098 n-C₆H₁₃ n-C₄H₉ 1099 n-C₆H₁₃ n-C₅H₁₁ 1100 n-C₆H₁₃ n-C₆H₁₃ 1101 n-C₆H₁₃ n-C₇H₁₅ 1102 n-C₇H₁₅ CH₃ 1103 n-C₇H₁₅ C₂H₅ 1104 n-C₇H₁₅ n-C₃H₇ 1105 n-C₇H₁₅ n-C₄H₉ 1106 n-C₇H₁₅ n-C₅H₁₁ 1107 n-C₇H₁₅ n-C₆H₁₃ 1108 n-C₇H₁₅ n-C₇H₁₅ 1109 CH₃O CH₃ 1110 CH₃O C₂H₅ 1111 CH₃O n-C₃H₇ 1112 CH₃O n-C₄H₉ 1113 CH₃O n-C₅H₁₁ 1114 CH₃O n-C₆H₁₃ 1115 CH₃O n-C₇H₁₅ 1116 C₂H₅O CH₃ 1117 C₂H₅O C₂H₅ 1118 C₂H₅O n-C₃H₇ 1119 C₂H₅O n-C₄H₉ 1120 C₂H₅O n-C₅H₁₁ 1121 C₂H₅O n-C₆H₁₃ 1122 C₂H₅O n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 1123 to 1185

The following are prepared from 36 analogously to Example 9:

No. R¹ R² Phase sequence T/° C. 1123 CH₃ CH₃ 1124 CH₃ C₂H₅ 1125 CH₃ n-C₃H₇ 1126 CH₃ n-C₄H₉ 1127 CH₃ n-C₅H₁₁ 1128 CH₃ n-C₆H₁₃ 1129 CH₃ n-C₇H₁₅ 1130 C₂H₅ CH₃ 1131 C₂H₅ C₂H₅ 1132 C₂H₅ n-C₃H₇ 1133 C₂H₅ n-C₄H₉ 1134 C₂H₅ n-C₅H₁₁ 1135 C₂H₅ n-C₆H₁₃ 1136 C₂H₅ n-C₇H₁₅ 1137 n-C₃H₇ CH₃ 1138 n-C₃H₇ C₂H₅ 1139 n-C₃H₇ n-C₃H₇ 1140 n-C₃H₇ n-C₄H₉ 1141 n-C₃H₇ n-C₅H₁₁ 1142 n-C₃H₇ n-C₆H₁₃ 1143 n-C₃H₇ n-C₇H₁₅ 1144 n-C₄H₉ CH₃ 1145 n-C₄H₉ C₂H₅ 1146 n-C₄H₉ n-C₃H₇ 1147 n-C₄H₉ n-C₄H₉ 1144 n-C₄H₉ n-C₅H₁₁ 1149 n-C₄H₉ n-C₆H₁₃ 1150 n-C₄H₉ n-C₇H₁₅ 1151 n-C₅H₁₁ CH₃ 1152 n-C₅H₁₁ C₂H₅ 1153 n-C₅H₁₁ n-C₃H₇ 1154 n-C₅H₁₁ n-C₄H₉ 1155 n-C₅H₁₁ n-C₅H₁₁ 1156 n-C₅H₁₁ n-C₆H₁₃ 1157 n-C₅H₁₁ n-C₇H₁₅ 1158 n-C₆H₁₃ CH₃ 1159 n-C₆H₁₃ C₂H₅ 1160 n-C₆H₁₃ n-C₃H₇ 1161 n-C₆H₁₃ n-C₄H₉ 1162 n-C₆H₁₃ n-C₅H₁₁ 1163 n-C₆H₁₃ n-C₆H₁₃ 1164 n-C₆H₁₃ n-C₇H₁₅ 1165 n-C₇H₁₅ CH₃ 1166 n-C₇H₁₅ C₂H₅ 1167 n-C₇H₁₅ n-C₃H₇ 1168 n-C₇H₁₅ n-C₄H₉ 1169 n-C₇H₁₅ n-C₅H₁₁ 1170 n-C₇H₁₅ n-C₆H₁₃ 1171 n-C₇H₁₅ n-C₇H₁₅ 1172 CH₃O CH₃ 1173 CH₃O C₂H₅ 1174 CH₃O n-C₃H₇ 1175 CH₃O n-C₄H₉ 1176 CH₃O n-C₅H₁₁ 1177 CH₃O n-C₆H₁₃ 1178 CH₃O n-C₇H₁₅ 1179 C₂H₅O CH₃ 1180 C₂H₅O C₂H₅ 1181 C₂H₅O n-C₃H₇ 1182 C₂H₅O n-C₄H₉ 1183 C₂H₅O n-C₅H₁₁ 1184 C₂H₅O n-C₆H₁₃ 1185 C₂H₅O n-C₇H₁₅ Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding EP Patent Application No. 06025029.7, filed on Dec. 4, 2006, are incorporated by reference herein.

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. 

1. A compound of formula I

in which R¹ and R² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂ or an alkyl group having 1 to 15 C atoms, which is optionally monosubstituted by CN or CF₃ or at least monosubstituted by halogen and in which optionally one or more CH₂ groups, in each case independently of one another, are replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

 —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither 0 nor S atoms are linked directly to one another, >Y¹Y²— denotes >C═CH— or >CH—CH₂—, L¹ and L² each, independently of one another, denote H, halogen, —CN or —CF₃,

and  each, independently of one another, and, if present more than once, these also independently of one another, denote (a) a trans-1,4-cyclohexylene radical, in which one or two non-adjacent CH₂ groups are optionally replaced by —O— and/or —S, (b) a 1,4-cyclohexenylene radical, (c) a 1,4-phenylene radical, in which one or two non-adjacent CH groups are optionally replaced by N, (d) naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or (e) 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene or spiro[3.3]heptane-2,6-diyl, wherein in (a) and (b), one or more —CH₂— groups, independently of one another, are optionally replaced by a —CHF— or a —CF₂— group, and in (c) and (d), one or more —CH═ groups, independently of one another, are optionally replaced by —CF═, —CCl═, —CBr═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(OCH₃)═, —C(OCHF₂)═ or —C(OCF₃)═, Z¹ and Z² each, independently of one another, and, if present more than once, these also independently of one another, denote a single bond, —CH₂—CH₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—, or —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and n and m each independently denote 0, 1, 2 or 3, where (n+m) denotes 0, 1, 2 or
 3. 2. A compound according to claim 1, which is of formula 1A


3. A compound according to claim 1, which is of formula IB


4. A compound according to claim 1, wherein L¹ and L² both denote F.
 5. A compound according to claim 1, wherein Z¹ and Z² denote a single bond.
 6. A compound according to claim 1, wherein (m+n) denotes 0 or
 1. 7. A compound according to claim 1, wherein (m+n) denotes
 0. 8. A liquid-crystal medium, comprising a compound according to claim
 1. 9. A liquid-crystal medium according to claim 8, which has a nematic phase.
 10. A liquid-crystal medium according to claim 8, which comprises one or more dielectrically negative compounds of formula II

in which R²¹ and R²² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂ or an alkyl group having 1 to 15 C atoms, which is optionally monosubstituted by CN or CF₃ or at least monosubstituted by halogen and in which optionally one or more CH₂ groups, in each case independently of one another, are replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

 —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither 0 nor S atoms are linked directly to one another, Z²¹ and Z²² each, independently of one another, and, if present more than once, these also independently of one another, denote a single bond, —CH₂—CH₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—, or —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and

 each, independently of one another, denote

L²¹ and L²² both denote C—F or one of the two denotes N and the other denotes C—F, and I denotes 0 or
 1. 11. A liquid-crystal medium according to claim 10, which comprises one or more compounds of formula II-1

in which R²¹, R²², Z¹² Z²²

and I have the meanings given for compounds of formula II.
 12. An electro-optical display, containing a liquid-crystal medium according to claim
 8. 13. A display according to claim 12, which is a VAN LCD.
 14. A process for preparing a liquid-crystal medium according to claim 8, comprising mixing one or more compounds of formula I with one or more further compounds.
 15. A process for preparing an electro-optical display, comprising introducing a liquid-crystal medium according to claim 8 between two substrates. 